CN104962281A - Benzoxazolyl based CuN2P2 orange phosphorescent material - Google Patents
Benzoxazolyl based CuN2P2 orange phosphorescent material Download PDFInfo
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- CN104962281A CN104962281A CN201510353071.4A CN201510353071A CN104962281A CN 104962281 A CN104962281 A CN 104962281A CN 201510353071 A CN201510353071 A CN 201510353071A CN 104962281 A CN104962281 A CN 104962281A
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- xantphos
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- quinoline
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Abstract
The invention discloses a benzoxazolyl based CuN2P2 orange phosphorescent material and a preparation method. The phosphorescent complex of the benzoxazolyl based CuN2P2 orange phosphorescent material is obtained through cuprous salt and ligand complexation, a molecular structure of the phosphorescent complex is [Cu(2-QBO)(Xantphos)]PF6, the 2-QBO and the Xantphos in the formula are respectively electrically neutral bidentate chelating ligand 2-(2-benzoxazole) quinoline and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene. The complex has the advantages that micro-molecules are easy to purify and luminous efficiency is high and has high heat stability. The benzoxazolyl based CuN2P2 orange phosphorescent material is obtained through direct mixing and reaction of Cu(CH3CN)4PF6 and a dichloromethane solution of the complex, has the advantages that a process is simple and convenient, a device is simple, raw materials are easy to obtain, cost is low and the like, can serve as an orange photo-luminescent material and can also serve as a luminous-layer phosphorescent material consisting of multiple layers of organic materials and used in an electroluminescent device.
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-EmittingDiode 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 electroluminescent material that can be used for OLED has fluorescent material and phosphor material two kinds.Because electroluminescent process produces the singlet excitons of 25% and the feature of 75% triplet exciton, and fluorescent material can only utilize singlet excitons, phosphor material then can utilize singlet excitons and triplet exciton and luminous simultaneously, and therefore the research and development of phosphor material seem particularly important.
The research and development object of phosphor material is all generally Metal-organic complex small molecule material instead of organic molecule, and reason is pure organic molecule, and at room temperature phosphorescence is very weak, can not detect phosphorescent emissions even at all.And title complex small molecule material can realize phosphorescent emissions easily, and can realize high efficiency luminescence, being also easy to preparation and purifying, being easy to be made into film, is therefore that a unique class is actually used in the phosphor material of OLED product luminescent layer at present.The phosphorescent substance that current OLED product adopts is the title complex containing the precious metal such as iridium, rhenium, and they have shown good use properties and market manifestation.But there is cost intensive in such precious metals complex, the especially problem of environmental risk.Therefore, research and development at present for base metal Cu (I) complex phosphorescence material receive much concern, Cu (I) title complex is very cheap, without environmental 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 orange 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, the price of its costliness also has influence on applying of OLED the finished product and market manifestation.With Cu (I) title complex as orange 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, does not just still reach application demand in its luminous intensity of OLED operating temperature range.Therefore Cu (I) the title complex orange phosphor 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 orange phosphor Cu (I) complex luminescent material and preparation method thereof.By the solution coordination reaction of Cu (I) ion and organic ligand, facilitate and prepared the Cu of luminescent properties and good thermal stability (I) complex luminescent material at an easy rate, its orange (partially red) phosphorescence luminous intensity is very large, 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, is to provide a kind of orange (partially red) phosphorescence Cu (I) complex luminescent material newly, by Cu (CH
3cN)
4pF
6carry out coordination reaction with part to obtain, its molecular structure is [Cu (2-QBO) (Xantphos)] PF
6; In formula, Xantphos and 2-QBO is respectively electric neutrality part 4,5-two (diphenylphosphine)-9,9-dimethyl xanthene and 2-(2-benzoxazole) quinoline.
Described part 2-(2-benzoxazole) quinoline, be the combination of benzoxazole and quinoline, its molecular structure is such as formula (I):
O in described part in benzoxazole structure has neither part nor lot in coordination, and atom N in atom N and quinoline structure and cuprous ion form Bidentate State.
Described luminescent material is oblique system, P2
1/ c spacer, unit cell parameters is
α=90 °, β=110.093 (7) °, γ=90 °,
z=4, D
c=1.3928g/cm
3, crystal color is orange; This luminescent material structure shows as ionic complex, and wherein hexafluoro-phosphate radical is counter anion, and positively charged ion is then the coordination cation formed by cuprous ion and part 2-QBO, Xantphos complexing; In this coordination cation, cuprous ion adopts CuN2P2 tetrahedral coordination mode, and wherein two N come from benzoxazole group in a double-tooth chelate ligand 2-QBO and quinoline group respectively, and two P come from another double-tooth chelate ligand Xantphos; Its molecular structure is such as formula (II):
Described luminescent material is applied to orange light phosphor material, this material is subject to the UV-light of very wide wavelength region (300-550nm) or exciting of visible ray, very strong orange (partially red) light can be sent, its maximum emission wavelength is 607nm, chromaticity coordinates value is (0.5808,0.4180), luminescent lifetime is 7 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 a kind of orange (partially red) phosphorescence Cu (I) complex luminescent material [Cu (2-QBO) (Xantphos)] PF
6preparation method.This preparation method is by Cu (CH
3cN)
4pF
6there is coordination reaction with the dichloromethane solution mixing of two kinds of parts, finally revolve steaming and produce the crystal powder of product and realize.Its specific embodiments is divided into five steps:
(1) under room temperature by Cu (CH
3cN)
4pF
6powder is dissolved in methylene dichloride completely, obtains colorless cleared solution;
(2) under room temperature, Xantphos is dissolved in methylene dichloride, obtains colorless cleared solution;
(3) under room temperature, 2-QBO is dissolved in methylene dichloride, fully stirs, obtain yellow clear solution;
(4) will mix by three kinds of solution above, and fully stir generation coordination reaction;
(5) will react gained solution steams to dry at normal temperature decompression backspin, and 100 degree lower dry, obtains crystalline orange powder product.
In preparation method of the present invention, the mol ratio Cu (CH of described three kinds of reactants
3cN)
4pF
6: Xantphos: 2-QBO is 1: 1: 1.
First beneficial effect of the present invention is provided orange (partially red) phosphorescence Cu (I) complex luminescent material [Cu (2-QBO) (Xantphos)] PF
6the benzoxazole group wherein introduced and quinoline group are conducive to molecular-excited state luminescence, Ni metal effectively promotes intersystem crossing to the existence of the charge transtion (MLCT) of part, and Cu (I) around part exist sterically hindered can the non-radiative decay of Inhibitory molecules excited state, X ligand antphos and 2-QBO forms firmly chelating ligands with cuprous ion, and the part of aromatic ring all has very large rigidity characteristic more than two kinds, the thus 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 and thermostability, for the further application of luminescent material provides technical support.
Secondly beneficial effect of the present invention is preparation orange (partially red) phosphorescence Cu (I) complex luminescent material [Cu (2-QBO) (Xantphos)] PF
6method, have simple process, equipment used is simple, and 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. phosphorescent complexes [Cu (2-QBO) (Xantphos)] PF
6the single crystal structure figure of molecule.
Fig. 2. phosphorescent complexes [Cu (2-QBO) (Xantphos)] PF
6molecule is in unit cell and the accumulation graph of peripheral space.
Fig. 3. phosphorescent complexes [Cu (2-QBO) (Xantphos)] PF
6x-ray powder diffraction: (a) be according in embodiment 2 single crystal structural data calculate obtain spectrogram; B () is the collection of illustrative plates of gained powder in the embodiment of the present invention 1.
Fig. 4. phosphorescent complexes [Cu (2-QBO) (Xantphos)] PF
6ultraviolet-ray visible absorbing (UV-Vis) spectrogram.
Fig. 5. title complex [Cu (2-QBO) (Xantphos)] PF
6the light emission spectrogram (right side) of crystallite sample under 420 nano wave length optical excitation; With measure under 607 nanometer supervisory wavelength excite spectrogram (left side).
Embodiment
The performance of implementation procedure of the present invention and material is illustrated by embodiment:
Embodiment 1
A large amount of Cu (I) title complex [Cu (2-QBO) (Xantphos)] PF
6the preparation of the crystallite sample: [Cu (CH taking 0.1mmol (37.3mg)
3cN)
4] PF
6be dissolved in 5mL CH
2cl
2in, then take the Xantphos (4,5-two (diphenylphosphine)-9,9-dimethyl xanthene) of 2-QBO and 0.1mmol (57.9mg) of 0.1mmol (27.3mg) successively, be dissolved in 5mLCH respectively
2cl
2in, by all three kinds of solution mixing (mol ratio of described three kinds of reactants is 1: 1: 1), and stirring makes it fully coordination reaction to occur, finally gained yellow solution is filtered, and revolve all solvents of steaming removing, 100 degree dry, obtains orange crystal powder and be product, productive rate 97% (in Cu).
Embodiment 2
Synthesis Cu (I) title complex [Cu (2-QBO) (Xantphos)] PF
6monocrystalline: take 37mg Cu (CH
3cN)
4pF
6be dissolved in after in 10mL methylene dichloride with the Xantphos part of 58mg, the dichloromethane solution again 5mL being contained the 2-QBO part of 28mg once adds in above-mentioned solution, stirring makes it to dissolve rear filtration completely, filtrate covers Virahol and impels product crystallization, after leaving standstill a couple of days, separate out a large amount of orange bulk crystals.The orange crystal selecting a 0.33mm × 0.30mm × 0.26mm size is used for x-ray crystal structure test.The molecular structure of this compound is illustrated in accompanying drawing 1, and its structure cell packed structures is illustrated in accompanying drawing 2.
To title complex [Cu (2-QBO) (Xantphos)] PF
6pure phase crystal prototype carried out a series of performance test.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, strong orange (partially red) light can be launched, chromaticity coordinates value is (0.5808,0.4180), concrete excitation spectrum and emmission spectrum are as shown in Figure 5.And the transient state fluorometric investigation of this material is shown, its luminescent lifetime is 7 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 phosphor material of OLED luminescent layer.
Claims (4)
1., based on a cuprous title complex orange phosphor material for benzoxazolyl quinoline part, it is characterized in that: the structural formula of luminescent material is [Cu (2-QBO) (Xantphos)] PF
6, in formula, Xantphos is electric neutrality biphosphine ligand 4,5-two (diphenylphosphine)-9,9-dimethyl xanthene; In formula, 2-QBO is neutral heterocyclic ligand 2-(2-benzoxazole) quinoline, and this part is the combination of benzoxazole and quinoline, and its molecular structure is such as formula (I):
Under room temperature, this complex luminescent material is oblique system, P2
1/ c spacer, unit cell parameters is
α=90 °, β=110.093 (7) °, γ=90 °,
z=4, D
c=1.3928g/cm
3, crystal color is orange; This luminescent material structure shows as ionic complex, and wherein hexafluoro-phosphate radical is counter anion, and positively charged ion is then the coordination cation formed by cuprous ion and part 2-QBO, Xantphos complexing; In this coordination cation, cuprous ion adopts CuN
2p
2tetrahedral coordination mode, wherein two N come from benzoxazole group in a double-tooth chelate ligand 2-QBO and quinoline group respectively, and two P come from another double-tooth chelate ligand Xantphos; Its molecular structure is such as formula (II):
2. the preparation method of Cu (I) title complex orange phosphor material according to claim 1, the method comprises the following steps:
(1) under room temperature by Cu (CH
3cN)
4pF
6powder is dissolved in methylene dichloride completely, obtains colorless cleared solution;
(2) under room temperature, Xantphos is dissolved in methylene dichloride, obtains colorless cleared solution;
(3) under room temperature, 2-QBO is dissolved in methylene dichloride, fully stirs, obtain yellow clear solution;
(4) will mix by three kinds of solution above, and fully stir generation coordination reaction;
(5) will react gained solution steams to dry at normal temperature decompression backspin, and 100 degree lower dry, obtains crystalline orange powder product.
3. the preparation method of Cu (I) title complex orange phosphor material according to claim 2, is characterized in that: the mol ratio Cu (CH of described three kinds of reactants
3cN)
4pF
6: Xantphos: 2-QBO is 1: 1: 1.
4. the application of Cu (I) title complex orange phosphor material according to claim 1, it is characterized in that described luminescent material has maximum emission peak at 607nm place, can be used as embedded photoluminescent material, or be used as the light emitting layer luminesces material in multilayer electroluminescent device.
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Cited By (3)
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| CN106967121A (en) * | 2017-03-21 | 2017-07-21 | 中国计量大学 | A kind of cuprous complex yellow phosphorescence luminescent material of 8 hydroxyl quinaldines |
| CN108794534A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex orange phosphor luminescent material of BINAP and PBO mixtures |
| CN114591365A (en) * | 2022-03-22 | 2022-06-07 | 郑州大学 | Light-emitting copper compound based on benzimidazole phosphine oxide ligand and preparation method and application thereof |
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| CN103834384A (en) * | 2014-03-20 | 2014-06-04 | 中国计量学院 | New crystal form of benzoxazolyl quinoline cuprous complex luminescent material |
| CN104059065A (en) * | 2014-05-30 | 2014-09-24 | 浙江工业大学 | phenanthroline derivative and preparation method and application thereof |
| CN104099086A (en) * | 2014-07-14 | 2014-10-15 | 中国计量学院 | Novel crystal-form Cu (I) complex luminescent material adopting benzoxazolyl quinoline 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 |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103833777A (en) * | 2014-03-20 | 2014-06-04 | 中国计量学院 | Benzoxazolylquinoline ligand-based cuprous complex luminescent material |
| CN103834384A (en) * | 2014-03-20 | 2014-06-04 | 中国计量学院 | New crystal form of benzoxazolyl quinoline cuprous complex luminescent material |
| CN104059065A (en) * | 2014-05-30 | 2014-09-24 | 浙江工业大学 | phenanthroline derivative and preparation method and application thereof |
| CN104099086A (en) * | 2014-07-14 | 2014-10-15 | 中国计量学院 | Novel crystal-form Cu (I) complex luminescent material adopting benzoxazolyl quinoline 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106967121A (en) * | 2017-03-21 | 2017-07-21 | 中国计量大学 | A kind of cuprous complex yellow phosphorescence luminescent material of 8 hydroxyl quinaldines |
| CN108794534A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex orange phosphor luminescent material of BINAP and PBO mixtures |
| CN114591365A (en) * | 2022-03-22 | 2022-06-07 | 郑州大学 | Light-emitting copper compound based on benzimidazole phosphine oxide ligand and preparation method and application thereof |
| CN114591365B (en) * | 2022-03-22 | 2023-09-05 | 郑州大学 | Luminous copper compound based on benzimidazole phosphine oxide ligand and preparation method and application thereof |
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