CN103626789A - Binuclear cuprous complex luminescent material and preparation method thereof - Google Patents
Binuclear cuprous complex luminescent material and preparation method thereof Download PDFInfo
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- CN103626789A CN103626789A CN201310611365.3A CN201310611365A CN103626789A CN 103626789 A CN103626789 A CN 103626789A CN 201310611365 A CN201310611365 A CN 201310611365A CN 103626789 A CN103626789 A CN 103626789A
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Abstract
The invention discloses a binuclear Cu(I) complex luminescent material capable of emitting green light and a preparation method of the binuclear Cu(I) complex luminescent material. The green luminescent complex is obtained by complexing cuprous bromide and a ligand, and the molecular structure is [Cu(POP)Br]2, wherein the POP in the formula is an electric neutrality ligand bis(2-diphenyl phosphorus phenyl)ether, and the binuclear structure molecule is formed by coupling a bridging ligand bromide ion with two metal ions. The complex has the advantages that the micromolecule is easy to purify and the luminous efficiency is high, and the heat stability is high. The material is obtained by directly mixing and reacting the cuprous bromide with a dichloromethane solution of the ligand, the process is simple and convenient, the equipment is simple, the raw material is easy to obtain and the cost is low. The material can be used as a photoluminescence green material, and can be further used as a luminescent layer green material in an electroluminescent device composed 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, particularly relate to field of organic electroluminescent materials.
Background technology
Along with technology is growing, the functional materials with special light physics, photochemical properties is more and more studied, wherein with Ir, and Pt, Ru, Re, the precious metals complex such as Os and organic compound are as a kind of novel luminescent material and by extensive concern.Yet because these transition metal are expensive, content is low, exploitation difficulty, thus limited their large-scale application in real life, production.Therefore, work out comparatively cheap metal complexes photoelectric functional material and just seem particularly important.For precious metal, copper has cheapness, environmental protection, the advantage such as nontoxic, and China's copper resource reserve is abundant, occupies third place in the world.Therefore, the research based on the luminous novel material of univalent copper complex, has very important theory significance and actual application value.
Construct the part of lighting function Cu (I) title complex, mainly with the atoms such as N, P, S, ethylene linkage, acetylene bond or atomic group, be dentate greatly, can be monodentate, bidentate or multiple tooth, can be rigidity or flexibility, they have changeable coordination mode, the common title complex of constructing as Nitrogen-Containing Heterocyclic Ligand.Meanwhile, there is the constitutional features of monokaryon, double-core and even multinuclear in the molecular structure of this class Cu (I) title complex, and common monokaryon is main with 3,4 coordinations, forms trilateral or positive tetrahedron type coordination ball, the endorsing and form square or ladder shape structure as four of multinuclear.Some part, under different condition, has different coordination modes, has also just produced the title complex of different in kind, and the effect of this " several satellite in a rocket " is attracting numerous scientists always.As can be seen here, various alternative of its part, structure various rich, has given such luminescent material very large development space.
In electroluminescent process, after hole and electron recombination, singlet state and triplet exciton produce simultaneously, according to spin Statistical Principles, the ratio of triplet state and singlet state exciton number is 3:1, because the radiative transition of triplet exciton is prohibited, the triplet exciton luminous efficiency of most of organic materials is very low, so the top efficiency of organic electroluminescence device can not surpass 25%, for triplet energies is utilized effectively, the exploitation of phosphor material has become the current focus towards electroluminescent investigation of materials naturally.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, thereby change quantity of radiant energy, improves the luminescent quantum productive rate of phosphorescence, and be easy to realize the polychrome transmittings such as red, yellow, green, blue.Aspect electrophosphorescence device, obtaining certain trial in recent years.
At present, luminous efficiency and the thermal stability of Cu (I) complex luminescent material are not high enough, and the RGB tri-look materials of superior performance are rare, and this remains restriction, and it obtains the key issue of application at key areas such as organic electroluminescents.Therefore research and develop all good Cu (I) complex luminescent materials of luminous efficiency and thermostability, for related industrieies such as exploitation OELD, all have important practical significance.
Summary of the invention
The object of the present invention is to provide high-luminous-efficiency and green luminescent material better performances for RGB three primary colours, and preparation method thereof.This double-core Cu (I) title complex is under solution reaction condition, by two (2-diphenylphosphine) phenylates (being POP) of part, CuBr hybrid reaction, is obtained, 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 green 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 double-core Cu (I) complex luminescent material, carries out coordination reaction obtain by CuBr and part, and its molecular structural formula is [Cu (POP) Br]
2, ion centered by the univalent copper ion in formula, part is phosphorus-containing ligand POP and halide-ions Br
-.
Described luminescent material is oblique system, C2/c (No.15) spacer, and unit cell parameters is
α=90 °, β=98.241 (7) °, γ=90 °,
z=4, D
c=1.484g/cm
3, outward appearance shows as the block transparent crystals of light green; Single crystal structure demonstration, title complex shows as the dual-core architecture that four phosphorus atom coordinations on two Cu (I) atoms and two Br atoms and two POP parts form, and two Cu (I) in molecule adopt CuBr
2p
2tetrahedral coordination pattern, wherein two P come from the POP part of a bidentate chelating, and two Br are the bromide anions that doube bridge connects, just by these two Br
-the bridging of ion, two CuBr
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 luminescent material is applied to green light luminescent material, this material is subject to the UV-light of very wide wavelength region (250-450nm) or exciting of visible ray, can send very strong green light, and its maximum emission wavelength is 485nm, chromaticity coordinates value is (0.201,0.3179).
Luminescent layer green light material in the electroluminescent device that described green light luminescent material forms as multilayer organic materials.
Two of technical scheme of the present invention, is to provide a kind of preparation method of described title complex, and the method is the solution coordination reaction by CuBr and part POP, and reduction vaporization obtains micro-crystalline product and realizes.Its specific embodiments is divided into three steps:
(1) under room temperature, two (2-diphenylphosphine) phenylates are poured in bottle, added enough methylene dichloride, fully stir, obtain colorless cleared solution A;
(2) under room temperature, in A solution, add pure cuprous bromide powder, the mol ratio of cuprous bromide and two (2-diphenylphosphine) phenylates is 1:1, under nitrogen atmosphere, fully stirs, and 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 gained solution rotary evaporation under reduced pressure, obtain white micro-crystals, be drying to obtain Cu (I) complex luminescent material product.
The invention has the beneficial effects as follows first a kind of novel double-core Cu (I) 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; In two (2-diphenylphosphine phenyl) ether part, 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 suppressed 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 non-radiative decay that excited state distortion causes; Therefore this material presents strong green emission feature under ultraviolet excitation, for the further application of the green light luminescent material in OLED in fields such as organic electroluminescents provides technical support.
Secondly beneficial effect of the present invention is the described dinuclear complex luminescent material [Cu (POP) Br] 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.
Accompanying drawing explanation
Fig. 1. be double-core Cu of the present invention (I) complex luminescent material [Cu (POP) Br]
2the single crystal structure figure of molecule.
Fig. 2. double-core Cu (I) complex luminescent material [Cu (POP) Br]
2the unit cell packed structures figure of molecule.
Fig. 3. be the double-core in embodiment 1 [Cu (POP) Br]
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 Cu (I) complex luminescent material [Cu (POP) Br]
2uV, visible light absorb light collection of illustrative plates, X-coordinate represents wavelength, ordinate zou represents absorbancy.
Fig. 5. be double-core Cu (I) complex luminescent material [Cu (POP) Br]
2thermogravimetric analysis curve, X-coordinate represents temperature, ordinate zou represents weight percentage.
Fig. 6. be double-core Cu (I) complex luminescent material [Cu (POP) Br]
2exciting light collection of illustrative plates, supervisory wavelength is 485nm, gained maximum excitation wavelength is 377nm; X-coordinate is wavelength, and ordinate zou is intensity.
Fig. 7. be double-core Cu (I) complex luminescent material [Cu (POP) Br]
2utilizing emitted light collection of illustrative plates, excitation wavelength is 377nm, maximum emission peak is positioned at 485nm place; X-coordinate is wavelength, and ordinate zou is intensity.
Embodiment
The present invention is a kind of double-core Cu (I) complex luminescent material and preparation method thereof, clear and definite wherein title complex [Cu (POP) Br]
2molecular structure and space accumulation mode, and the luminescent properties of material and thermostability.Embodiment is as follows:
Embodiment 1
Double-core Cu (I) title complex [Cu (POP) Br]
2preparation:
1) respectively take the POP of 0.3mmol, pour in Shenlek bottle, add 30ml methylene dichloride, inflated with nitrogen, fully stirs, and obtains settled solution A;
2) with stoichiometric ratio 1:1, take the CuBr of 0.3mmol, pour in solution 1, 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 [Cu (POP) Br]
2.
Double-core Cu (I) title complex [Cu (POP) Br]
2the acquisition of monocrystalline and sign:
The acquisition of monocrystalline adopts solvent diffusion method, takes [Cu (POP) Br] 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), standing a couple of days, obtain water white transparency bulk crystals, select the single crystal that a size is 0.38 * 0.32 * 0.26mm and be used for X ray single crystal diffraction, resolve and obtain [Cu (POP) Br]
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 [Cu (POP) Br]
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 5.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 green light, and chromaticity coordinates value is (0.201,0.3179), and concrete excitation spectrum and emmission spectrum are as shown in accompanying drawing 6 and accompanying drawing 7.This material can be applicable to the green light luminescent material of ultraviolet excitation, is also applicable to the green light material of OLED luminescent layer.
Claims (5)
1. double-core Cu (I) complex luminescent material, is characterized in that: the structural formula of luminescent material is [Cu (POP) Br]
2, in formula, POP is that electric neutrality contains two (the 2-diphenylphosphine phenyl) ether of P part, in two metal ions of abutment part bromide anion connection, is formed centrally dual-core architecture molecule; Described luminescent material is oblique system, C2/c (No.15) spacer, and unit cell parameters is
α=90 °, β=98.241 (7) °, γ=90 °,
z=4, D
c=1.484g/cm
3, outward appearance shows as the block transparent crystals of light green; Single crystal structure demonstration, title complex shows as the dual-core architecture that four phosphorus atom coordinations on two Cu (I) atoms and two Br atoms and two POP parts form, and two Cu (I) in molecule adopt CuBr
2p
2tetrahedral coordination pattern, wherein two P come from the POP part of a bidentate chelating, and two Br are the bromide anions that doube bridge connects, just by these two Br
-the bridging of ion, two CuBr
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 dinuclear complex is suc as formula (I):
2. the preparation method of double-core Cu (I) complex luminescent material according to claim 1, the method comprises the following steps:
(1) under room temperature, two (2-diphenylphosphine) phenylates are poured in bottle, added enough methylene dichloride, fully stir, obtain colorless cleared solution A;
(2) under room temperature, in A solution, add cuprous bromide powder, the mol ratio of cuprous bromide and two (2-diphenylphosphine) phenylates 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 gained solution rotary evaporation under reduced pressure, obtain white micro-crystals, be drying to obtain Cu (I) complex luminescent material product.
3. the preparation method of double-core Cu (I) complex luminescent material according to claim 2, is characterized in that: the mol ratio CuBr:POP of described two kinds of reactants is 1:1.
4. the application of double-core Cu (I) complex luminescent material according to claim 1, is characterized in that described luminescent material is applied to green emitting embedded photoluminescent material.
5. the application of double-core Cu (I) complex luminescent material according to claim 1, is characterized in that described luminescent material is as the luminescent layer green luminescent material in the electroluminescent device of multilayer organic materials composition.
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| CN104140808A (en) * | 2014-06-10 | 2014-11-12 | 中国计量学院 | Tetrahedral cuprous complex luminescent material containing oxazolyl pyridine ligands |
| 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 |
| CN105733565A (en) * | 2016-04-18 | 2016-07-06 | 中国计量大学 | Benzoxazolyl isoquinoline cuprous complex luminous material |
| CN105754591A (en) * | 2016-04-18 | 2016-07-13 | 中国计量大学 | Crystal form of benzoxazolyl isoquinoline cuprous complex luminescent material |
| CN105838356A (en) * | 2016-05-05 | 2016-08-10 | 中国计量大学 | CuBrN2P type cuprous complex orange luminescent material based on benzoxazolyl pyridine |
| CN114409699A (en) * | 2022-01-24 | 2022-04-29 | 南京邮电大学 | Novel X-ray luminescent material and preparation method thereof |
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| 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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| 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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| CN105754591A (en) * | 2016-04-18 | 2016-07-13 | 中国计量大学 | Crystal form of benzoxazolyl isoquinoline cuprous complex luminescent material |
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| CN105838356A (en) * | 2016-05-05 | 2016-08-10 | 中国计量大学 | CuBrN2P type cuprous complex orange luminescent material based on benzoxazolyl pyridine |
| CN105838356B (en) * | 2016-05-05 | 2018-03-02 | 中国计量大学 | A kind of cuprous complex orange light emitting materials of CuBrN2P types based on benzoxazole yl pyridines |
| CN114409699A (en) * | 2022-01-24 | 2022-04-29 | 南京邮电大学 | Novel X-ray luminescent material and preparation method thereof |
| CN114409699B (en) * | 2022-01-24 | 2023-10-20 | 南京邮电大学 | Novel X-ray luminescent material and preparation method thereof |
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Application publication date: 20140312 |