CN104861961A - CuIN2P tetrahedral coordination cuprous complex luminous material - Google Patents
CuIN2P tetrahedral coordination cuprous complex luminous material Download PDFInfo
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- CN104861961A CN104861961A CN201510277839.4A CN201510277839A CN104861961A CN 104861961 A CN104861961 A CN 104861961A CN 201510277839 A CN201510277839 A CN 201510277839A CN 104861961 A CN104861961 A CN 104861961A
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Abstract
The invention discloses an orange phosphorescent CuIN2P cuprous complex luminous material and a preparation method of the luminous material. The phosphorescent complex is obtained by coordination reaction of cuprous iodide and a ligand, and has a molecular structural formula of CuI(2-PBO)(TXP-2,4), wherein 2-PBO and TXP-2,4 are electrically neutral ligands 2-(2-benzoxazole) pyridine and tri-(2,4xylyl) phosphine. The complex has the advantages that the complex is micromolecular and easy in purification, has high luminous efficiency and can be dissolved by an organic solvent easily. The material is obtained by directly mixing cuprous iodide and a ligand solution for reaction, and has the advantages of simple technology, simple equipment, easy availability of raw materials, low cost and the like. The material can serve as a photoluminescent orange material and a phosphorescent material of a luminous layer in an electroluminescent device consisting of a plurality 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
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, thus the generation of acquisition energy excites and is finally directed at luminous phenomenon.Uv-radiation, visible ray and ir radiation etc. all can cause photoluminescence.Embedded photoluminescent material can be used for the aspects such as the scintillator in fluorometric analysis, traffic sign, tracking monitor, agricultural light conversion film, nuclear detection technology, the fluorescence optical collector in solar energy converting technology.Electroluminescent (electroluminescent, be called for short EL), refers to that luminescent material is under electric field action, and being subject to the phenomenon of electric current and exciting of electric field and luminescence, is a kind of luminescence process electric energy being directly converted to luminous energy.There is the material of this performance, automatically controlled luminescent device can be made into, such as photodiode (LED) and Organic Light Emitting Diode (Organic Light-Emitting Diode is called for short OLED).And the large series products of LED and OLED two, in the flat pannel display of advanced person and solid-state energy-saving illumination field, all there is very tempting application prospect, and shown its good industrialized development impetus at present.
Can produce electroluminescent solid material has a variety of, mainly comprises inorganic semiconductor material, organic small molecule material, macromolecular material and title complex small molecule material.Due to OLED there is energy-conservation, frivolous, free from glare, without ultraviolet, 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 the problem of visible angle, can manufacture on the substrate of unlike material, can make the many merits such as the product that can bend, and enjoys attracting attention of scientific and technological circle and industrial community in recent years.And along with the development of society, OLED technology (or by) colour TV, mobile phone, various indicating meter, various illumination with or the field such as display terminal of the military equipment such as decorative lamp, aircraft obtain using more and more widely.
The principle of work of OLED is under the effect of extra electric field, and hole and electronics from positive and negative electrode injection device, are compounded to form exciton at luminescent layer respectively, luminous by the attenuation of exciton.And according to spin statistics principle, singlet excitons and triplet exciton respectively account for 25% and 75%, so utilize merely the luminescent layer that fluorescent material makes, to can only utilize at most the input energy of 25%, other most of energy then can bring serious pyrogenic effect, not only wastes energy but also is unfavorable for the long-time stable work of device.It is different from the fluorescent material of singlet excitons energy can only be utilized, transition metal complex phosphor material is owing to having very strong SO coupling effect, the all input energy comprising triplet state and triplet state can be made full use of, fundamentally breach 25% energy limited existed in a very long time, increase substantially the efficiency of OLED, that is, utilize transition metal complex phosphor material that the internal quantum of OLED can be made to reach 100%.Therefore, in the luminescent material based on OLED is studied, the research and development of phosphor material seem particularly important.
More specifically analyze, with the precious metals complex such as Ir, Pt, Ru, Re, Os and organic compound as a kind of novel luminescent material by extensive concern.OLED phosphor material on sale is at present all the title complex of precious metal iridium and platinum etc., although they are existing performance preferably in performance, these transition metal are expensive, and content is low, exploitation difficulty, limit in certain limit they real life, produce in large-scale application.Therefore, find novel cheap metal complexes photoelectric functional material and just seem extremely important.For precious metal, copper has cheapness, environmental protection, the advantage such as nontoxic, and China's copper resource reserve enriches, and occupies third place in the world.Therefore, based on the research of the luminous novel material of univalent copper complex, there is very important theory significance and actual application value.With Cu (I) title complex as phosphor material then long-standing (N.Armaroli, G.Accorsi, F.Cardinali, A.Listorti, Top.Curr.Chem.2007,280,69-115.), Cu (I) complex luminescent material of this cheapness can be prepared easily by Cu (I) ion and suitable organic ligand.The part of Cu (I) can be monodentate, bidentate or multiple tooth, rigidity or flexibility.There is changeable coordination mode, the ligancy that plurality of optional is selected.Simultaneously there is the structure of monokaryon, double-core and even multinuclear in its space structure, and common monokaryon is with 3, and 4 coordinations are main, forms trilateral or positive tetrahedron type, multinuclear endorse formation square as four.Just the current luminous intensity at OLED operating temperature range Cu (I) complex phosphorescence material does not still reach application demand.Therefore Cu (I) the complex phosphorescence material of development of new cheapness has great actual application value.
Summary of the invention
The object of this invention is to provide a kind of new cuprous complex luminescent material of orange phosphor CuIN2P type and preparation method thereof.By the solution coordination reaction of cuprous iodide and organic ligand, facilitate and prepared the good cuprous complex luminescent material of tetrahedral coordination CuIN2P type of luminescent properties at an easy rate, its orange phosphor luminous intensity is very large, thermostability might as well, and its decay of luminescence feature meets the requirement of OLED to material phosphorescence luminescent lifetime very much, is applied to the reduction that OLED emitting layer material is conducive to product cost.
One of technical scheme of the present invention, be to provide a kind of new cuprous complex luminescent material of orange phosphor CuIN2P type, carry out coordination reaction by cuprous iodide and part to obtain, its molecular structural formula is CuI (2-PBO) (TXP-2,4), 2-PBO and TXP-2 in formula, 4 are respectively electroneutral containing P part three (2,4-xylyl) phosphine and heterocyclic ligand 2-(2-benzoxazole) pyridine.
Described part 2-(2-benzoxazole) pyridine, be the combination of benzoxazole and pyridine, its molecular structure is such as formula (I):
A N in described part in benzoxazoles structure and an atom N on pyridine ring and cuprous ion form the coordination mode of bidentate chelating.
Described luminescent material is rhombic system, Pbca spacer, unit cell parameters
α=90 °, β=90 °, γ=90 °,
z=8, D
c=1.436g/cm
3, crystal color is yellow, and profile is block; Title complex shows as the cuprous title complex of electroneutral tetrahedral coordination CuIN2P type, and Cu (I) wherein adopts CuIN
2p tetrahedral four-coordination pattern, two N come from pyridine groups in the 2-PBO part of a bidentate chelating and benzoxazole group respectively, and a P comes from an end group TXP-2,4 parts; The molecular structure of described luminescent material is such as formula (II):
Described luminescent material is applied to orange-colored light phosphor material, this material is subject to the UV-light of very wide wavelength region (300-500nm) or exciting of visible ray, very strong orange-colored light can be sent, its maximum emission wavelength is 620nm, chromaticity coordinates value is (0.5944,0.4048), luminescent lifetime is 3 microseconds.
Described orange phosphor luminescent material is used as the luminescent layer phosphor material in the electroluminescent device of multilayer organic materials composition.
Technical scheme two of the present invention, is to provide the preparation method of the cuprous complex luminescent material CuI (2-PBO) (TXP-2,4) of a kind of orange phosphor CuIN2P type.There is coordination reaction after being mixed with the solution of part by cuprous iodide in this preparation method, is then removed by solvent thus separate out the crystal of product and realize.Its specific embodiments is divided into five steps:
(1) under room temperature, the powder of cuprous iodide is dissolved completely in acetonitrile;
(2) under room temperature, the powder of part three (2,4-xylyl) phosphine is dissolved in methylene dichloride completely;
(3) by described two kinds of solution mixing, and stir and make it that coordination reaction fully occurs and obtain solution A;
(4) in solution A, add the acetonitrile solution of 2-PBO, and stirring makes it fully coordination reaction to occur;
(5) reaction solution is steamed at vacuumized conditions backspin, except namely desolventizing obtains yellow fine crystals product.
In preparation method of the present invention, mol ratio CuI: 2-PBO: TXP-2,4 of described three kinds of reactants are 1: 1: 1.
First beneficial effect of the present invention is the provided cuprous complex luminescent material CuI (2-PBO) of orange phosphor CuIN2P type (TXP-2,4), wherein the existence of halogen iodine can change the excited state composition of molecule, make to add the charge transtion composition of very large halogen to part in Ni metal to charge transtion (MLCT) excited state of part, and new (X+M) CT excited state effectively can not only promote intersystem crossing and effectively can suppress the non-radiative decay of excited state; And the Phosphine ligands three (2 of methyl is contained in adjacency pair position on the other hand, 4-xylyl) to cause Cu (I) around to exist larger sterically hindered for phosphine, can the tetrahedral coordination configuration of stable complex molecule well, thus the non-radiative decay of Inhibitory molecules excited state, thus the phosphorescent emissions performance that had of this molecular material.This complex material had both possessed the cheap advantage with being easy to purifying, and had good solvability, thermostability, for the further application of luminescent material provides technical support.
Beneficial effect of the present invention, next prepares the cuprous complex luminescent material CuI (2-PBO) of orange phosphor CuIN2P type (TXP-2,4) method, there is simple process, equipment used is simple, raw material is simple and easy to get, and production cost is low, can obtain having the advantages such as the product of very high yield in a short period of time.
Accompanying drawing explanation
Fig. 1. the single crystal structure figure of phosphorescent complexes CuI (2-PBO) (TXP-2,4).
Fig. 2. phosphorescent complexes CuI (2-PBO) (TXP-2,4) is in unit cell and peripheral space accumulation graph.
Fig. 3. the X-ray powder diffraction of phosphorescent complexes CuI (2-PBO) (TXP-2,4): (a) calculates according to single crystal structural data in embodiment 2 spectrogram obtained; B () is the collection of illustrative plates of gained powder in the embodiment of the present invention 1.
Fig. 4. the thermogravimetric-differential scanning calorimetric analysis curve of phosphorescent complexes CuI (2-PBO) (TXP-2,4), X-coordinate represents temperature, and ordinate zou represents weight percentage (left side) and thermal change (right side).
Fig. 5. ultraviolet-ray visible absorbing (UV-Vis) spectrogram of phosphorescent complexes CuI (2-PBO) (TXP-2,4).
Fig. 6. what title complex CuI (2-PBO) (TXP-2,4) crystallite sample measured under 620 nanometer supervisory wavelength excites spectrogram.
Fig. 7. the light emission spectrogram of title complex CuI (2-PBO) (TXP-2,4) crystallite sample under 420 nano wave length optical excitation.
Embodiment
The performance of implementation procedure of the present invention and material is illustrated by embodiment:
Embodiment 1
The preparation of a large amount of crystallite samples: the CuI taking 0.5mmol is dissolved in 10mL acetonitrile, take 0.5 three (2,4-xylyl) Phosphine ligands is dissolved in the methylene dichloride of 8mL, and by these two kinds of solution mixing, and stir and make it that coordination reaction fully occurs and obtain colourless solution A; Then the 2-PBO part taking 0.5mmol is dissolved in 8mL acetonitrile, then this solution is added in above-mentioned solution A, and stirring makes it fully coordination reaction to occur, finally gained yellow reaction liquid is revolved and steam all solvents of removing, vacuum-drying, obtain yellow crystalline powder and be product, productive rate 96% (in Cu).
Embodiment 2
The cuprous title complex CuI (2-PBO) of synthesis phosphorescence (TXP-2,4) monocrystalline: the CuI taking 0.1mmol is dissolved in 3mL acetonitrile, take 0.1 three (2,4-xylyl) Phosphine ligands is dissolved in the methylene dichloride of 3mL, by this two kinds of solution mixing, and stir and make it that coordination reaction fully occurs and obtain colourless solution A; Then the 2-PBO part taking 0.1mmol is dissolved in 2mL acetonitrile, then this solution is added in above-mentioned solution A, and stirring makes it fully coordination reaction to occur, finally gained yellow solution is filtered, filtrate covers normal hexane and impels product crystallization, after leaving standstill a couple of days, separate out a large amount of yellow tabular crystal.The yellow sheet transparent crystals selecting a 0.36mm × 0.33mm × 0.15mm size is used for the structured testing of X-ray single crystal diffraction.The molecular structure of this compound is illustrated in accompanying drawing 1, and its structure cell packed structures is illustrated in accompanying drawing 2.
A series of performance test has been carried out to the pure phase crystal prototype of the cuprous title complex CuI (2-PBO) (TXP-2,4) of phosphorescence.Thermogravimetric (TG) and means of differential scanning calorimetry (DSC) test show that this material has good stability, as shown in Figure 4.Steady-state fluorescence test has been carried out to material crystals of the present invention, result shows that this material is under different excitation wavelength effects, can launch strong orange-colored light, and chromaticity coordinates value is (0.5944,0.4048), concrete excitation spectrum and emmission spectrum are as shown in accompanying drawing 6 and accompanying drawing 7.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 be applicable to the orange phosphor material that multi-wavelength excites, and is also suitable for very much the orange-colored light phosphor material of OLED luminescent layer.
Claims (5)
1. the cuprous complex luminescent material of orange phosphor CuIN2P type, it is characterized in that: the structural formula of luminescent material is CuI (2-PBO) (TXP-2,4), TXP-2 in formula, 4 for electric neutrality is containing P part three (2,4-xylyl) phosphine; In formula, 2-PBO is electric neutrality heterocyclic ligand 2-(2-benzoxazole) pyridine, and this part is the combination of benzoxazole and pyridine, and its molecular structure is such as formula (I):
Described luminescent material is rhombic system, Pbca spacer, unit cell parameters
α=90 °, β=90 °, γ=90 °,
z=8, D
c=1.436g/cm
3, crystal color is yellow, and profile is block; Title complex shows as the cuprous title complex of electroneutral tetrahedral coordination CuIN2P type, and Cu (I) wherein adopts CuIN
2p tetrahedral four-coordination pattern, two N come from pyridine groups in the 2-PBO part of a bidentate chelating and benzoxazole group respectively, and a P comes from an end group TXP-2,4 parts; The molecular structure of described luminescent material is such as formula (II):
2. the preparation method of the cuprous complex luminescent material of orange phosphor CuIN2P type according to claim 1, the method comprises the following steps:
(1) under room temperature, the powder of cuprous iodide is dissolved completely in acetonitrile;
(2) under room temperature, the powder of part three (2,4-xylyl) phosphine is dissolved in methylene dichloride completely;
(3) by described two kinds of solution mixing, and stir and make it that coordination reaction fully occurs and obtain solution A;
(4) in solution A, add the acetonitrile solution of 2-PBO, and stirring makes it fully coordination reaction to occur;
(5) reaction solution is steamed at vacuumized conditions backspin, except namely desolventizing obtains yellow fine crystals product.
3. the preparation method of the cuprous complex luminescent material of orange phosphor CuIN2P type according to claim 2, is characterized in that: mol ratio CuI: 2-PBO: TXP-2,4 of described three kinds of reactants are 1: 1: 1.
4. the application of the cuprous complex luminescent material of orange phosphor CuIN2P type according to claim 1, is characterized in that described luminescent material is used as orange-colored light embedded photoluminescent material.
5. the application of the cuprous complex luminescent material of orange phosphor CuIN2P type according to claim 1, is characterized in that described luminescent material is used as the luminescent layer phosphor material in the electroluminescent device of multilayer organic materials composition.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105777785A (en) * | 2016-05-05 | 2016-07-20 | 中国计量大学 | Cuprous iodide complex luminescent material based on benzoxazolyl pyridine and cyclohexyldiphenylphosphine |
| CN105801877A (en) * | 2016-05-05 | 2016-07-27 | 中国计量大学 | Organic/inorganic hybridized cuprous iodine anion high-polymeric chain-based semiconductor material |
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| WO2012156378A1 (en) * | 2011-05-13 | 2012-11-22 | Cynora Gmbh | Copper(i) complexes, in particular for optoelectronic components |
| CN102876320A (en) * | 2012-10-10 | 2013-01-16 | 中国计量学院 | Cuprous complex luminescent material and preparation method thereof |
| CN103588794A (en) * | 2013-11-22 | 2014-02-19 | 中国计量学院 | Cuprous complex luminescence material and preparation method thereof |
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| WO2012156378A1 (en) * | 2011-05-13 | 2012-11-22 | Cynora Gmbh | Copper(i) complexes, in particular for optoelectronic components |
| CN102876320A (en) * | 2012-10-10 | 2013-01-16 | 中国计量学院 | Cuprous complex luminescent material and preparation method thereof |
| CN103588794A (en) * | 2013-11-22 | 2014-02-19 | 中国计量学院 | Cuprous complex luminescence material and preparation method thereof |
Non-Patent Citations (2)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105777785A (en) * | 2016-05-05 | 2016-07-20 | 中国计量大学 | Cuprous iodide complex luminescent material based on benzoxazolyl pyridine and cyclohexyldiphenylphosphine |
| CN105801877A (en) * | 2016-05-05 | 2016-07-27 | 中国计量大学 | Organic/inorganic hybridized cuprous iodine anion high-polymeric chain-based semiconductor material |
| CN105801877B (en) * | 2016-05-05 | 2018-12-11 | 中国计量大学 | A kind of high poly chain base semiconductor material of cuprous iodine anion of organic inorganic hybridization |
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