CN103865523A - Double-core cuprous iodide complex luminescent material - Google Patents
Double-core cuprous iodide complex luminescent material Download PDFInfo
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- CN103865523A CN103865523A CN201410076371.8A CN201410076371A CN103865523A CN 103865523 A CN103865523 A CN 103865523A CN 201410076371 A CN201410076371 A CN 201410076371A CN 103865523 A CN103865523 A CN 103865523A
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- cuprous iodide
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Abstract
The invention discloses a blue-light-emitting double-core cuprous iodide complex luminescent material and a preparation method thereof. The blue-light-emitting complex is obtained by complexing cuprous iodide and ligand, and has a molecular structure of [CuI(DPPP)]2, wherein DPPP in the formula is electrically neutral P ligand-containing 1,5-di(diphenyl phosphine) pentane; two metal ion centers are combined by bridging ligand iodide ions to form a double-core structural molecule. The complex has the advantages that small molecules are easy to extract and high in luminous efficiency and has high thermal stability. The material is obtained by directly mixing and reacting the cuprous iodide and the dichloromethane solution of the ligand, and has the advantages of simple and convenient process, simple equipment, readily available raw materials, low cost and the like. The material can be used as a photoluminescent blue-light-emitting material, and can also be used as a blue-light material for a luminescent layer in an electroluminescent device consisting of a plurality of layers of organic materials.
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
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, excites and be finally directed at luminous phenomenon thereby obtain power generation.Embedded photoluminescent material can be used for the aspects such as the fluorescence optical collector in fluorometric analysis, traffic sign, tracking monitor, solar energy converting technology.Electroluminescent (electroluminescent is called for short EL), refers to that luminescent material is under electric field action, is subject to electric current and exciting of electric field and luminous phenomenon.There is the material of this performance, can be made into automatically controlled luminescent device, for example photodiode (LED) and Organic Light Emitting Diode (OLED).Due to OLED there is energy-conservation, frivolous, free from glare, without ultraviolet ray, 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 visible angle problem, can on the substrate of unlike material, manufacture, can make can bending the many merits such as product, enjoy in recent years attracting attention of scientific and technological circle and industrial community.And along with social development, OLED technology (or by) colour TV, mobile phone, various indicating meter, various illumination with or the field such as the 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 two kinds of fluorescent material and phosphor materials.Due to the singlet state exciton of electroluminescent process generation 25% and the feature of 75% triplet exciton, and fluorescent material can only utilize singlet state exciton, phosphor material can utilize singlet state exciton and triplet exciton and luminous simultaneously, and therefore the research and development of phosphor material seem particularly important.Have been found that at present, can there is multiple transition of electron mode in the univalent copper complex of atom centered by copper, as metal-ligand transfer transport, part-metal electron shifts, transfer transport between part, multiple transition of electron or the transition combinations such as the interior transfer transport of part, thus change quantity of radiant energy, improve the luminescent quantum productive rate of phosphorescence, and be easy to realize the polychrome transmittings such as red, yellow, green, blue.And with respect to the title complex containing precious metals such as iridium, rheniums, univalent copper complex also has aboundresources, cheapness, without advantages such as environmental risks, Cu (I) complex luminescent material of therefore researching and developing novel excellent property is significant and good market application foreground.
But for current EL market application, luminous efficiency and the thermal stability of Cu (I) complex luminescent material are not high enough, and the material of superior performance is rare, this remains restriction, and it obtains the key issue of applying at key areas such as organic electroluminescents.Therefore research and develop all good Cu (I) complex luminescent materials of luminous efficiency and thermostability, all have important practical significance for related industrieies such as exploitation OELD.
Summary of the invention
The object of the present invention is to provide a kind of dinuclear complex luminescent material based on cuprous iodide and preparation method thereof.This double-core Cu (I) title complex is under solution reaction condition, and by ligand 1, two (diphenylphosphine) pentanes (being DPPP) of 5-, CuI hybrid reaction obtain, and its simple synthetic method is easily gone, production cost is low.This double-core Cu (I) complex luminescent material luminescent properties and good thermal stability, its blue light luminous intensity is very large, can be used as candidate material and is applied to photoluminescence or electroluminescent field.
One of technical scheme of the present invention, is to provide a kind of dinuclear complex luminescent material based on cuprous iodide, carries out coordination reaction obtain by CuI and part, and its molecular structural formula is [CuI (DPPP)]
2, ion centered by the univalent copper ion in formula, part is phosphorus-containing ligand DPPP and halide-ions I
-.
Described double-core cuprous iodide complex luminescent material is triclinic(crystalline)system, P-1 (No.2) spacer, and unit cell parameters is
d
c=1.543g/cm
3, outward appearance shows as colourless block transparent crystals; Single crystal structure demonstration, title complex shows as the dual-core architecture that four phosphorus atom coordinations on two Cu (I) atoms and two iodine atoms and two DPPP parts form, and two Cu (I) in molecule adopt Cul
2p
2tetrahedral coordination pattern, wherein two P come from the DPPP part of a bidentate chelating, and two I are the iodide ions that doube bridge connects, just by these two I
-the bridging of ion, two Cul
2p
2tetrahedron has formed the dual-core architecture on common limit, and this dual-core architecture has strengthened rigidity and the stability of agent structure, is conducive to the transmitting of triplet state and the raising of luminous efficiency; The molecular structure of described title complex is suc as formula (I):
Described double-core cuprous iodide complex luminescent material is applied to blue light luminescent material, this material is subject to the UV-light of very wide wavelength region (350-450nm) or exciting of visible ray, can send very strong blue light, its maximum emission wavelength is 465nm, chromaticity coordinates value is (0.1416,0.2353).
Described complex luminescent material is as the luminescent layer blue light material in the electroluminescent device of multilayer organic materials composition.
Two of technical scheme of the present invention, is to provide a kind of preparation method of described double-core cuprous iodide complex luminescent material, and the method is the solution coordination reaction by CuI and part DPPP, and reduction vaporization obtains micro-crystalline product and realizes.Its specific embodiments is in three steps:
(1) under room temperature, two 1,5-(diphenylphosphine) pentanes are poured in bottle, added enough methylene dichloride, fully stir,
Colorless cleared solution A;
(2) under room temperature, in A solution, add pure cuprous iodide powder, the mol ratio of two (diphenylphosphine) pentanes of cuprous iodide and 1,5-is 1
:1, under nitrogen atmosphere, fully stir, reacting at normal temperature without light 6h, obtains colourless micro-turbid solution B;
(3) under room temperature by B solution filter, obtain the settled solution that contains product, then, by under reduced pressure rotary evaporation of gained solution, obtain white micro-crystals, be drying to obtain dinuclear complex luminescent material product.
The invention has the beneficial effects as follows first a kind of novel double-core cuprous iodide complex luminescent material is provided, this neutral Cu (I) complex phosphorescence material obviously has higher anti-susceptibility to oxygen molecule, can make device more stable, and efficiency is higher; 1, in two (diphenylphosphine) pentane parts of 5-, P atom has stronger to characteristic electron, also have the halogen anion in structure also to have to characteristic electron, the transfer transport mode of whole title complex is changed, effectively suppress the structural aberration of excited state molecule, energy transfer efficiency is got a promotion, thereby improve the luminous efficiency of material; Meanwhile, two (2-diphenylphosphine) phenylate parts of large steric hindrance are also conducive to suppress the excited state non-radiative decay causing that distorts; Therefore this material presents strong blue emission feature under ultraviolet excitation, for the blue light emitting material in OLED provides technical support in the further application in the fields such as organic electroluminescent.
Secondly beneficial effect of the present invention is the described dinuclear complex luminescent material [CuI (DPPP)] of preparation
2method, there is simple process, equipment used is simple, raw material is simple and easy to get, production cost is low, high productivity obtains the advantage of a large amount of products in a short period of time.
Brief description of the drawings
Fig. 1. be double-core cuprous iodide complex luminescent material of the present invention [CuI (DPPP)]
2the single crystal structure figure of molecule.
Fig. 2. double-core cuprous iodide complex luminescent material [CuI (DPPP)]
2the unit cell packed structures figure of molecule.
Fig. 3. be the double-core in embodiment 1 [CuI (DPPP)]
2the X-ray powder diffraction figure of luminescent material crystallite, X-coordinate represents diffraction angle scale, ordinate zou represents intensity scale.
Fig. 4. be double-core cuprous iodide complex luminescent material [CuI (DPPP)]
2fourier transform infrared light collection of illustrative plates, X-coordinate represents wave number, ordinate zou represents transmitance.
Fig. 5. be double-core cuprous iodide complex luminescent material [CuI (DPPP)]
2uV, visible light absorb light collection of illustrative plates, X-coordinate represents wavelength, ordinate zou represents absorbancy.
Fig. 6. be double-core cuprous iodide complex luminescent material [CuI (DPPP)]
2thermogravimetric and poor formula scanning amount thermal analysis curve, X-coordinate represents temperature, ordinate zou represents weight percentage (left side) and thermal change (right side).
Fig. 7. be double-core cuprous iodide complex luminescent material [CuI (DPPP)]
2excitation spectrum (left side) figure, supervisory wavelength is 465nm, gained maximum excitation wavelength is 388nm; And emmission spectrum (right side) figure, excitation wavelength is 388nm, maximum emission peak is positioned at 465nm place; X-coordinate is wavelength, and ordinate zou is intensity.
Embodiment
The present invention is a kind of double-core cuprous iodide complex luminescent material and preparation method thereof, clear and definite wherein title complex [CuI (DPPP)]
2molecular structure and space accumulation mode, and the luminescent properties of material and thermostability.Embodiment is as follows:
Embodiment 1
Double-core cuprous iodide title complex [CuI (DPPP)]
2preparation:
1) respectively take the DPPP of 0.3mmol, pour in Shenlek bottle, add 30ml methylene dichloride, inflated with nitrogen, fully stirs, and obtains settled solution A;
2) take the CuI of 0.3mmol at 1: 1 with stoichiometric ratio, pour in solution A, continue to react under the atmosphere of nitrogen, lucifuge stirs 6 hours, obtains colourless micro-turbid solution B;
3) solution B is filtered, gets its filtrate, by filtrate under reduced pressure rotary evaporation except desolventizing, obtain white micro-crystals powdery product, dry, obtain Cu (I) complex luminescent material [CuI (DPPP)]
2.
Double-core cuprous iodide title complex [CuI (DPPP)]
2the acquisition of monocrystalline and sign:
The acquisition of monocrystalline adopts solvent diffusion method, takes [CuI (DPPP)] of 0.1mmol
2powder, be dissolved in the methylene dichloride of 1ml, be placed in small test tube, slowly add Virahol (volume ratio of Virahol and dichloromethane solution is 1.5: 1), leave standstill a couple of days, obtain water white transparency bulk crystals, select the single crystal that a size is 0.20 × 0.13 × 0.12mm and be used for X ray single crystal diffraction, resolve and obtain [CuI (DPPP)]
2molecular structure.The molecular structure of this compound is illustrated in accompanying drawing 1, and unit cell packed structures is illustrated in accompanying drawing 2.
To dinuclear complex [CuI (DPPP)]
2pure phase crystal prototype carried out a series of performance tests.TG test shows that this material has good thermostability, and its initial decomposition temperature reaches 300 degrees Celsius, sees accompanying drawing 6.Material crystals of the present invention has been carried out to steady-state fluorescence test, and result shows that this material, under ultraviolet excitation, launches strong blue light, and chromaticity coordinates value is (0.1416,0.2353), and concrete excitation spectrum and emmission spectrum are as shown in Figure 7.This material can be applicable to the blue light luminescent material of ultraviolet excitation, is also applicable to the blue light material of OLED luminescent layer.
Claims (5)
1. a double-core cuprous iodide complex luminescent material, is characterized in that: the structural formula of luminescent material is [CuI (DPPP)]
2, in formula, DPPP is that electric neutrality contains P ligand 1, two (diphenylphosphine) pentanes of 5-are formed centrally dual-core architecture molecule in two metal ions of abutment part iodide ion connection; Described dinuclear complex luminescent material is triclinic(crystalline)system, P-1 (No.2) spacer, and unit cell parameters is
z=1, D
c=1.543g/cm
3, outward appearance shows as colourless block transparent crystals; Single crystal structure demonstration, title complex shows as the dual-core architecture that four phosphorus atom coordinations on two Cu (I) atoms and two iodine atoms and two DPPP parts form, and two Cu (I) in molecule adopt Cul
2p
2tetrahedral coordination pattern, wherein two P come from the DPPP part of a bidentate chelating, and two I are the iodide ions that doube bridge connects, just by these two I
-the bridging of ion, two Cul
2p
2tetrahedron has formed the dual-core architecture on common limit, and this dual-core architecture has strengthened rigidity and the stability of agent structure, is conducive to the transmitting of triplet state and the raising of luminous efficiency; The molecular structure of described title complex is suc as formula (I):
2. the preparation method of double-core cuprous iodide complex luminescent material according to claim 1, the method comprises the following steps:
(1) under room temperature, two 1,5-(diphenylphosphine) pentanes are poured in bottle, added enough methylene dichloride, fully stir, obtain colorless cleared solution A;
(2) under room temperature, in A solution, add cuprous iodide powder, the mol ratio of two (diphenylphosphine) pentanes of cuprous iodide and 1,5-is 1: 1, under nitrogen atmosphere, fully stirs, and reacting at normal temperature without light 6 hours, obtains colourless micro-turbid solution B;
(3) under room temperature by B solution filter, obtain the settled solution that contains product, then, by under reduced pressure rotary evaporation of gained solution, obtain white micro-crystals powder, be drying to obtain double-core cuprous iodide complex luminescent material.
3. the preparation method of double-core cuprous iodide complex luminescent material according to claim 2, is characterized in that: the mol ratio CuI:DPPP of described two kinds of reactants is 1
:1.
4. the application of double-core cuprous iodide complex luminescent material according to claim 1, is characterized in that described luminescent material is applied to blue-light-emitting embedded photoluminescent material.
5. the application of double-core cuprous iodide complex luminescent material according to claim 1, is characterized in that described luminescent material is as the luminescent layer blue emitting material in the electroluminescent device of multilayer organic materials composition.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341439A (en) * | 2014-11-10 | 2015-02-11 | 安徽大学 | Triphenylamine cuprous carboxylate complex with electrochemiluminescence property and preparation method thereof |
| CN104877673A (en) * | 2015-06-23 | 2015-09-02 | 江西理工大学 | Pyridine pyrazole dinuclear copper [1] complex luminescent material and preparation method |
| CN104893715A (en) * | 2015-05-21 | 2015-09-09 | 中国计量学院 | Copper iodide phosphorescent complex light-emitting material containing Cu4I4 cluster core |
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| WO2003040255A1 (en) * | 2001-11-09 | 2003-05-15 | Sk Corporation | Blue light-emitting polymer containing 9,10-diphenylanthracene moiety and electroluminescent device using the same |
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2014
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Patent Citations (4)
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| WO2003040255A1 (en) * | 2001-11-09 | 2003-05-15 | Sk Corporation | Blue light-emitting polymer containing 9,10-diphenylanthracene moiety and electroluminescent device using the same |
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| DANIEL VOLZ等: "Molecular Construction Kit for Tuning Solubility, Stability and Luminescence Properties: Heteroleptic MePyrPHOS-Copper Iodide-Complexes and their Application in Organic Light-Emitting Diodes", 《CHEM.MATER.》 * |
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| PARASKEVAS ASLANIDIS等: "Copper(I) Halide Complexes with 1,3-Propanebis(diphenylphosphine) and Heterocyclic Thione Ligands: Crystal and Electronic Structures (DFT) of [CuCl(pymtH)(dppp)], [CuBr(pymtH)(dppp)], and [Cu(í-I)(dppp)]2", 《INORG.CHEM.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341439A (en) * | 2014-11-10 | 2015-02-11 | 安徽大学 | Triphenylamine cuprous carboxylate complex with electrochemiluminescence property and preparation method thereof |
| CN104893715A (en) * | 2015-05-21 | 2015-09-09 | 中国计量学院 | Copper iodide phosphorescent complex light-emitting material containing Cu4I4 cluster core |
| CN104893715B (en) * | 2015-05-21 | 2017-01-11 | 中国计量学院 | Copper iodide phosphorescent complex light-emitting material containing Cu4I4 cluster core |
| CN104877673A (en) * | 2015-06-23 | 2015-09-02 | 江西理工大学 | Pyridine pyrazole dinuclear copper [1] complex luminescent material and preparation method |
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