CN102899029A - Luminescent material of cuprous iodide complex and preparation method thereof - Google Patents
Luminescent material of cuprous iodide complex and preparation method thereof Download PDFInfo
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- CN102899029A CN102899029A CN2012103414724A CN201210341472A CN102899029A CN 102899029 A CN102899029 A CN 102899029A CN 2012103414724 A CN2012103414724 A CN 2012103414724A CN 201210341472 A CN201210341472 A CN 201210341472A CN 102899029 A CN102899029 A CN 102899029A
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Abstract
The invention discloses a luminescent material of red-phosphorescence cuprous iodide complex and a preparation method thereof. The phosphorescence complex is obtained through complexation of CuI and a ligand, with a molecular structure of (CuIL)n, wherein L is the ligand, the ligand is electrically neutral heterocyclic ligand 4-(2-benzoxazolyl) pyridine, that is, the combination of the benzoxazolyl and the pyridine. Due to introducing the benzoxazolyl group beneficial to luminescence of molecular excited state and heavy halogen iodine beneficial to intersystem crossing of the excited state into the material, and promotion of the intersystem crossing by metal-to-ligand charge transfer, the material has relatively good phosphorescence performance. The material is obtained by the directly mixing reaction of the ligand with an acetonitrile solution of CuI, has advantages of simple technology, simple equipment, easily-available raw materials, low cost and good thermal stability, and can be used as a photoluminescence red-phosphorescence material, and a phosphorescent material of a luminous layer of an electroluminescent device composed of multilayer organic materials.
Description
Technical field
The present invention relates to the luminescent material technical field, relate to embedded photoluminescent material field and electroluminescent material field, particularly relate to field of organic electroluminescent materials.
Background technology
Material is acknowledged as one of three large pillars of modern social development.And luminescent material all has very widely application especially as a kind of important functional materials wherein in fields such as industry, agricultural, medical science, national defence.Concrete example, they can be used as white dyes, high-visibility pigment, fluorescence dye, fluorescent reagent, laser dyes, lamp phosphor etc.Society demand that various information are shown particularly, and under the energy dilemma background to energy-saving illumination in the urgent need to, promoted widely developing rapidly of luminescent material.
Distinguish from principle of luminosity, luminescent material comprises photoluminescence and electroluminescent two large class Application Areass.Photoluminescence refers to that object is subject to the irradiation of external light source, excites and finally be directed at luminous phenomenon thereby obtain power generation.Uv-radiation, visible light and ir radiation etc. all can cause photoluminescence.Embedded photoluminescent material can be used for the scintillator in fluorometric analysis, traffic sign, tracking monitor, agricultural light conversion film, the nuclear detection technology, the aspects such as fluorescence optical collector in the solar energy converting technology.Electroluminescent (electroluminescent, be called for short EL) refers to luminescent material under electric field action, is subject to electric current and exciting of electric field and luminous phenomenon is a kind of luminescence process that electric energy directly is converted to luminous energy.Material with this performance can be made into automatically controlled luminescent device, for example photodiode (LED) and Organic Light Emitting Diode (Organic Light-Emitting Diode is called for short OLED).And LED and OLED two large series products all have very tempting application prospect in advanced person's flat pannel display and solid-state energy-saving illumination field, and have demonstrated its good industrialized development impetus at present.
Can produce electroluminescent solid material has a variety ofly, mainly comprises inorganic semiconductor material, organic small molecule material, macromolecular material and title complex small molecule material.Because OLED has 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 make, can make at the substrate of unlike material can the crooked many merits such as product, enjoy in recent years attracting attention of scientific and technological circle and industrial community.And along with the development of society, the OLED technology (or will) colour TV, mobile phone, various indicating meter, various illumination with or the fields such as display terminal of the military equipments such as decorative lamp, aircraft obtain using more and more widely.Two kinds of fluorescent material and phosphor materials can be arranged for the electroluminescent material of OLED.Because the singlet state exciton of electroluminescent process generation 25% and the feature of 75% triplet exciton, and fluorescent material can only utilize the singlet state exciton, phosphor material then can utilize simultaneously singlet state exciton and triplet exciton and be luminous, so the research and development of phosphor material seem particularly important.
The research and development object of phosphor material generally all is Metal-organic complex small molecule material rather than organic molecule, and reason is pure organic molecule, and at room temperature phosphorescence is very weak, even can not detect phosphorescent emissions at all.And the title complex small molecule material can be realized phosphorescent emissions easily, and can realize high efficiency luminously, also is easy to preparation and purifying, is easy to be made into film, therefore is that a unique class is actually used in the phosphor material of OLED product luminescent layer at present.The phosphorescent substance that present OLED product adopts is the title complex that contains the precious metals such as iridium, rhenium, and they have shown preferably use properties and market manifestation.But such precious metals complex exists cost expensive, especially the problem of environmental risk.Therefore, the at present research and development for base metal Cu (I) complex phosphorescence material receive much concern, Cu (I) title complex is very cheap, without the environment risk, Cu (I) complex luminescent material of therefore researching and developing novel excellent property is significant and good market application foreground.
More specifically analyze, OLED on sale is the title complex of precious metal iridium and your Rare Earth Europium with red phosphorescence material at present, although they are in the existing preferably performance of performance, its expensive price also has influence on applying of OLED the finished product and market manifestation.With cuprous iodide basigamy compound as the red phosphorescence material (N.Armaroli that then is of long duration, G.Accorsi, F.Cardinali, A.Listorti, Top.Curr.Chem.2007,280,69-115.), the Cu of this cheapness (I) complex luminescent material can be prepared easily by cuprous iodide and suitable organic ligand, does not just still reach application demand in its luminous intensity of OLED operating temperature range.Therefore the cuprous iodide basigamy compound red phosphorescence material of development of new cheapness has great actual application value.
Summary of the invention
The purpose of this invention is to provide a kind of new red phosphorescent cuprous iodide basigamy compound luminescent material and preparation method thereof.Solution coordination reaction by organic ligand and cuprous iodide, make things convenient for and prepared at an easy rate the cuprous iodide basigamy compound luminescent material of luminescent properties and good thermal stability, its red phosphorescent luminous intensity is very large, and its decay of luminescence feature meets the OLED device to the requirement of material phosphorescence luminescent lifetime very much, is applied to the reduction that OLED luminescent layer material is conducive to product cost.
One of technical scheme of the present invention provides a kind of red phosphorescent cuprous iodide basigamy compound luminescent material, carries out coordination reaction with cuprous iodide and part and obtains, and its molecular structure is (CuIL)
n, L is part in the formula.
Described part is a kind of electroneutral heterocyclic ligand 4-(2-benzoxazole) pyridine, and this part is the combination of benzoxazole and pyridine, and its molecular structure is suc as formula (I):
O in the described part in the benzoxazole structure and N atom have neither part nor lot in coordination, and the N atom in the pyridine structure and cuprous ion coordination form the four-coordination Metal-organic complex, and the molecular structure of this title complex shows as the notch cuttype chain, and wherein Cu (I) adopts CuI
3N tetrahedral coordination pattern, wherein three I come from three abutment μ
3-I
-Ion, a N comes from the pyridine groups of a part; Its molecular structure is suc as formula (II):
Described luminescent material can be applicable to the ruddiness phosphor material, and this material is subject to the UV-light of very wide wavelength region (260-460nm) or exciting of visible light, can both send very strong ruddiness, and its center emission wavelength is 620nm, luminescent lifetime 0.35 microsecond.
Described red phosphorescent luminescent material can be used as the luminescent layer phosphor material in the electroluminescent device that the multilayer organic materials forms.
Two of technical scheme of the present invention provides a kind of red phosphorescent cuprous iodide basigamy compound luminescent material (CuIL)
nThe preparation method.This preparation method is the two kinds of acetonitrile solution mixed occurrences coordination reaction by CuI and ligand L, thereby the generation product precipitates powder and realizes.Its specific embodiments is divided into four steps:
(1) be dissolved in the CuI powder in the acetonitrile fully under the room temperature;
(2) be dissolved in the ligand L powder in the acetonitrile fully under the room temperature;
(3) described two kinds of acetonitrile solutions are mixed, and stirring makes it fully to occur coordination reaction;
(4) will react the gained turbid solution and filter, and precipitate with acetonitrile washing gained, drying obtains orange crystalline powdered product.
Among the preparation method of the present invention, the preferred feed ratio (mol ratio) of described CuI and ligand L is that 4: 1 to 1: 4 scope is interval, and best feed ratio is 1: 1.
Beneficial effect of the present invention at first is the red phosphorescent cuprous iodide basigamy compound luminescent material that provides, wherein introduced the heavy halogen atom iodine that is conducive to the luminous benzoxazole group of molecular-excited state and is conducive to occur between molecule singlet excited and the triplet excited state intersystem crossing, and metal Cu promotes intersystem crossing to the existence of the electric charge transition (MLCT) of part, thereby this molecular material has preferably phosphorescent emissions performance.This molecular material had both possessed cheap and had been easy to the advantage of purifying, and had good thermostability, for the further application of luminescent material provides technical support.
Secondly beneficial effect of the present invention is preparation red phosphorescent cuprous iodide basigamy compound luminescent material (CuIL)
nMethod, have simple process, equipment used is simple, raw material is simple and easy to, production cost is low, can obtain in a short period of time having the very advantages such as product of high yield.
Description of drawings
Fig. 1. phosphorescent complexes (CuIL)
nThe single crystal structure figure of asymmetric separate unit in the molecule.
Fig. 2. phosphorescent complexes (CuIL)
nThe notch cuttype chain-like structure figure of molecule.
Fig. 3. phosphorescent complexes (CuIL)
nMolecule is in unit cell and the accumulation graph of peripheral space.
Fig. 4. phosphorescent complexes (CuIL)
nTG-DTA analysis (TG-DSC) graphic representation.
Fig. 5. phosphorescent complexes (CuIL)
nUltraviolet-ray visible absorbing (UV-Vis) spectrogram.
Fig. 6. phosphorescent complexes (CuIL)
nLight emission spectrogram under the optical excitation of 365 nano wave lengths.
Fig. 7. phosphorescent complexes (CuIL)
nThat measures under 620 nanometer supervisory wavelength excites spectrogram.
Embodiment
The performance of implementation procedure of the present invention and material is illustrated by embodiment:
Embodiment 1
Synthetic cuprous iodide basigamy compound (CuIL)
nMonocrystalline: after taking by weighing 19mg CuI and 20mg ligand L and being dissolved in respectively in the 10mL acetonitrile, the solution of ligand L is covered on the CuI solution gently, separates out a large amount of orange pin styloids after leaving standstill a couple of days.The orange crystal of selecting a 0.29mm * 0.16mm * 0.04mm size is used for the x-ray crystal structure test.The molecular structure of this compound is illustrated in accompanying drawing 1 and 2, and its structure cell packed structures is illustrated in accompanying drawing 3.
Embodiment 2
After taking by weighing 456mg CuI and 117.7mg ligand L (mol ratio 4: 1) and being dissolved in respectively the 10mL acetonitrile, these two kinds of acetonitrile solutions are mixed, and stir and to make it fully to occur coordination reaction, along with the orange precipitation of separating out of reaction increases gradually, form at last orange turbid solution.To react the gained turbid solution and filter, and precipitate with acetonitrile washing gained, vacuum-drying obtains crystalline orange powder product, productive rate 23% (in CuI).
Embodiment 3
After taking by weighing 114mg CuI and 470.8mg ligand L (mol ratio 1: 4) and being dissolved in respectively the 10mL acetonitrile, these two kinds of acetonitrile solutions are mixed, and stir and to make it fully to occur coordination reaction, along with the orange precipitation of separating out of reaction increases gradually, form at last orange turbid solution.To react the gained turbid solution and filter, with acetonitrile washing gained precipitation, vacuum-drying obtains crystalline orange powder, productive rate 21% (in ligand L).
Embodiment 4
After taking by weighing 114mg CuI and 117.7mg ligand L (mol ratio 1: 1) and being dissolved in respectively the 10mL acetonitrile, these two kinds of acetonitrile solutions are mixed, and stir and to make it fully to occur coordination reaction, along with the orange precipitation of separating out of reaction increases gradually, form at last orange turbid solution.To react the gained turbid solution and filter, with acetonitrile washing gained precipitation, vacuum-drying obtains crystalline orange powder, productive rate 96% (in CuI).
To title complex (CuIL)
nThe pure phase powdered sample carried out a series of performance tests.The micro melting point test shows that its fusing point is 180 degrees centigrade.TG and DSC test show that this material has preferably thermostability, and its initial decomposition temperature reaches 200 degrees centigrade, does not have in the past other obvious heat deflections at its fusing point, sees accompanying drawing 4.Material powder of the present invention has been carried out the steady-state fluorescence test, and the result shows that this material under different excitation wavelength effects, can both launch strong pure ruddiness, and concrete emmission spectrum and excitation spectrum are shown in accompanying drawing 6 and accompanying drawing 7.As seen, this material can be applicable to the red phosphorescence material that the multi-wavelength excites.And the transient state fluorometric investigation of this material is shown, its luminescent lifetime is 0.35 microsecond, belongs to phosphorescent emissions, is suitable for very much the phosphor material of OLED luminescent layer.
Claims (5)
1. red phosphorescent cuprous iodide basigamy compound luminescent material is characterized in that: the structural formula of compound is (CuIL)
n, L is electric neutrality heterocyclic ligand 4-(2-benzoxazole) pyridine in the formula, and this part is the combination of benzoxazole and pyridine, and its molecular structure is suc as formula (I):
The single crystal of this compound adopts oblique system under the room temperature, C2 (No.5) spacer, and unit cell parameters a=22.401 (5), b=4.0952 (8),
β=115.50 (3) °,
Z=4, D
c=2.103g/cm
3, crystal color is orange; It is the notch cuttype chain compound that is formed by CuI and ligand L complexing; Cu in this compound (I) adopts CuI
3N tetrahedral coordination pattern, wherein three I come from three abutment μ
3-I
-Ion, a N comes from the pyridine groups of a part; Its molecular structure is suc as formula (II):
2. the preparation method of described red phosphorescent cuprous iodide basigamy compound luminescent material according to claim 1, the method may further comprise the steps:
(1) be dissolved in the CuI powder in the acetonitrile fully under the room temperature;
(2) be dissolved in the ligand L powder in the acetonitrile fully under the room temperature;
(3) described two kinds of acetonitrile solutions are mixed, and stirring makes it fully to occur coordination reaction;
(4) will react the gained turbid solution and filter, and precipitate with acetonitrile washing gained, drying obtains orange crystalline powdered product.
3. the preparation method of described red phosphorescent cuprous iodide basigamy compound luminescent material according to claim 1, it is characterized in that: the preferred feed ratio (mol ratio) of described CuI and ligand L is that 4: 1 to 1: 4 scope is interval.
4. the according to claim 1 application of described red phosphorescent cuprous iodide basigamy compound luminescent material, it is characterized in that described luminescent material can be applicable to embedded photoluminescent material, this material is subject to the optical excitation of very wide wavelength region (260-460nm), can both send very strong ruddiness, its center emission wavelength is 620nm, luminescent lifetime 0.35 microsecond.
5. the according to claim 1 application of described red phosphorescent cuprous iodide basigamy compound luminescent material is characterized in that described luminescent material can be used as the luminescent layer phosphor material in the electroluminescent device that the multilayer organic materials forms.
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| CN103694263A (en) * | 2013-12-31 | 2014-04-02 | 中国计量学院 | Zinc bromide complex light emitting material and preparation method thereof |
| CN103694261A (en) * | 2014-01-08 | 2014-04-02 | 刘国政 | Cluster-based coordination polymer employing in-situ ligand reaction 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 |
| CN104178131A (en) * | 2014-07-14 | 2014-12-03 | 中国计量学院 | Mixed cuprous complex luminescent material containing oxazolyl pyridine ligand |
| CN104830321A (en) * | 2015-05-21 | 2015-08-12 | 中国计量学院 | Three-coordination dual-core copper iodide complex light-emitting material |
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| CN104830321A (en) * | 2015-05-21 | 2015-08-12 | 中国计量学院 | Three-coordination dual-core copper iodide complex light-emitting material |
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