CN103833777B - A kind of cuprous complex luminescent material based on benzoxazolyl quinoline part - Google Patents
A kind of cuprous complex luminescent material based on benzoxazolyl quinoline part Download PDFInfo
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- CN103833777B CN103833777B CN201410110751.9A CN201410110751A CN103833777B CN 103833777 B CN103833777 B CN 103833777B CN 201410110751 A CN201410110751 A CN 201410110751A CN 103833777 B CN103833777 B CN 103833777B
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- luminescent material
- qbo
- complex
- quinoline
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Abstract
The invention discloses cuprous complex luminescent material of a kind of orange-yellow phosphorescence and preparation method thereof.Phosphorescent complexes of the present invention, is obtained by cuprous salt and ligand complex, and its molecular structure is [Cu (QBO) (PPh
3)
2] PF
6, PPh in formula
3be electric neutrality ligand triphenylphosphine and 2-(2-benzoxazoles) quinoline with QBO.Described title complex had both possessed the advantage that small molecules is easily purified and luminous efficiency is high, and had high thermostability.This material is by Cu (CH
3cN)
4pF
6obtain with the direct hybrid reaction of the dichloromethane solution of part, have that simple process, equipment are simple, raw material is easy to get and low cost and other advantages.This material can be used as the orange luminescent material of photoluminescence, also can be used as the luminescent layer phosphor material in the electroluminescent device of multilayer organic materials composition.
Description
Technical field
The present invention relates to field of light emitting materials, especially relate to cuprous complex luminescent material field.
Background technology
Along with science and technology is growing, photon day by day replaces electronics and becomes the carrier of information, and photonics, photochemistry and photonic material, as the technical support of information science, more and more cause the concern of scientific and technological circle.There is special optical physics, the functional materials of photochemical properties more and more studied, day by day show tempting application prospect in fields such as electroluminescent device (LED), optical pickocff, nonlinear optical materials (NLO).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.
The part of light function Cu (I) title complex, the atoms such as most N, P, S, ethylene linkage, acetylene bond or atomic group are dentate, can be monodentate, bidentate or multiple tooth, rigidity or flexibility.There is changeable coordination mode, the ligancy that plurality of optional is selected, common as Nitrogen-and Phosphorus-containing heterocycle chelant complex.Simultaneously there is the structure of monokaryon, double-core and even multinuclear in its space structure, and common monokaryon, based on 3,4 coordinations, forms trilateral or positive tetrahedron type, multinuclear endorse formation square as four.Some part, at different conditions, has different coordination modes, also just creates the title complex of different in kind, and the effect of this " several satellite in a rocket ", attracts numerous scientists always.As can be seen here, the various selective of its part, structure various rich, gives the space that it is very large.And because of its outstanding behaviours in optical physics and photochemistry, cuprous title complex is at light-converting material, and especially electroluminescent material field is subject to the attention of Chinese and foreign department scholar and relevant industry personage day by day.
In electroluminescent process, after hole and electron recombination, singlet state and triplet exciton produce simultaneously, according to spin statistics principle, the ratio of triplet state and singlet excitons number is 3: 1, because the radiative transition of triplet exciton is prohibited, the triplet exciton luminous efficiency of major part organic materials is very low, so the top efficiency of organic electroluminescence device (OEL) can not more than 25%, for making triplet energies be utilized effectively, the exploitation of phosphor material becomes current research focus.Centered by copper, the univalent copper complex of atom avoids the precious metals such as the iridium platinum using costliness and have environmental risk, multiple transition of electron mode can be there is in title complex, as metal-ligand transfer transport, ligand metal transfer transport, transfer transport between part, the multiple transition of electron such as transfer transport or transition combination in part.And by for material molecule internal structure and MO regulation and control thereof, interior lights physical process can be changed, thus reach the phosphorescence quantum yields of almost 100%, can the multicolor emission such as red, yellow, green, blue be realized simultaneously.Therefore, in electroluminescent device, achieve good development in recent years, tentatively achieve commercial application simultaneously.
At present, luminescent properties and the thermal stability aspect of Cu (I) complex luminescent material still need lifting of constantly bringing forth new ideas, and the RGB tri-look material of superior performance is also rare, this remains its key issue in key areas acquisition widespread uses such as organic electroluminescents of restriction.Analyze more specifically, OEL orange/yellow phosphorescence material on sale is at present all the title complex of precious metal iridium and platinum etc., although performance there is good performance, the price of costliness also has influence on applying of OEL the finished product and market manifestation.Cu (I) title complex is as orange/yellow phosphorescence material then long-standing (N.Armaroli, G.Accorsi, F.Cardinali, A.Listorti, Top.Curr.Chem.2007,280,69-115.), just luminescent properties does not reach demand, therefore researches and develops luminous efficiency and all good Cu (I) complex luminescent material of thermostability, all has important practical significance for related industrieies such as development OEL.
Summary of the invention
The object of the present invention is to provide a kind of orange-yellow luminescent material of cuprous title complex based on benzoxazolyl quinoline part and preparation method thereof.This Cu (I) title complex is under solution reaction condition, by mantoquita Cu (CH
3cN)
4pF
6, part 2-(2-benzoxazole) quinoline (QBO), triphenylphosphine hybrid reaction obtain, its simple synthetic method is easy, production cost is low, and it is applied to the reduction that OEL emitting layer material is conducive to product cost.
One of technical scheme of the present invention, is to provide a kind of orange-yellow phosphorescence Cu (I) complex luminescent material, it is characterized in that: with Cu (CH
3cN)
4pF
6carry out coordination reaction with part 2-(2-benzoxazole) quinoline and ligand triphenylphosphine to obtain, 2-(2-benzoxazole) quinoline (QBO) part is the combination of benzoxazole and quinoline, and its molecular structural formula is as shown in (I):
The molecular structural formula of described complex luminescent material is [Cu (QBO) (PPh3)
2] PF
6, ion centered by the univalent copper ion in formula, form coordinate bond with two nitrogen-atoms on the phosphorus on triphenylphosphine ligand and 2-(2-benzoxazole) quinoline, its molecular structural formula is as shown in (II):
Under room temperature, this complex luminescent material is oblique system, P2
1/ c (No.14) spacer, unit cell parameters is a=10.9661 (3)
b=30.3204 (10)
c=13.7541 (4)
α=90 °, β=98.732 (3) °, γ=90 °, V=4507.38 (8)
z=4, D
c=1.4013g/cm
3, monocrystalline is yellow block transparent crystals; 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 QBO, PPh3 complexing.Coordination cation is the chelating tetrahedral structure formed by a univalent copper ion and two atom N and two phosphorus atom coordinations.Single crystal structure shows, and the benzoxazole ring in QBO and quinoline ring also exist two angles of 2.3 degree, make its structure more stable, and experiment proves, along with the change of conditions environmental, as solvent polarity, the change of temperature, its luminescent properties will change, and can be used for detecting.
Described luminescent material is applied to orange smooth phosphor material, this material is subject to the UV-light of very wide wavelength region (250-500nm) or exciting of visible ray, can send very strong orange coloured light, and its maximum emission wavelength is 600nm, chromaticity coordinates value is (0.5485,0.4461).Described orange-yellow phosphorescent light-emitting materials 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 preparation method of described complex luminescent material, and the method is by Cu (CH
3cN)
4pF
6, there is coordination reaction and obtain in the dichloromethane solution mixing of part QBO and PPh3.Its specific embodiments is divided into four 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, triphenylphosphine is dissolved in methylene dichloride, obtains colorless cleared solution;
(3) under room temperature, 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 evaporate to dryness under 40 degree, 100 degree lower dry, obtains crystalline orange product powder.
In preparation method of the present invention, described Cu (CH
3cN)
4pF
6, the optimum charging ratio of part QBO and PPh3 is 1: 1: 2.
Beneficial effect of the present invention, first there is provided a kind of novel Cu (I) complex luminescent material, wherein introduce the benzoxazole group and quinoline group that are conducive to molecular-excited state luminescence, metallic copper to the existence of the charge transtion (MLCT) of part effectively promote be between pass through, part QBO molecule exist sterically hindered can the nonradiative transition of Inhibitory molecules excited state, make its this luminescent material have better phosphorescent emissions performance.This material excites at 440nm can launch strong yellow orange light down, and chromaticity coordinates value is (0.5485,0.4461).This molecular material possesses the advantage that pure organic molecule is easy to purify, and has higher thermostability than organic molecule, for yellow orange light OEL material provides technical support in the further application in the fields such as organic electroluminescent.
Secondly beneficial effect of the present invention is the complex luminescent material [Cu (QBO) (PPh3) described in preparation
2] 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 the advantage of a large amount of product by high productivity in a short period of time.
Accompanying drawing explanation
Fig. 1 is Cu of the present invention (I) complex luminescent material [Cu (QBO) (PPh3)
2] PF
6the single crystal structure figure of molecule;
Fig. 2 is Cu of the present invention (I) complex luminescent material [Cu (QBO) (PPh3)
2] PF
6the steric bulk figure of molecule;
Fig. 3 is according to [Cu (QBO) (PPh3) in embodiment 1
2] PF
6the X-ray powder diffraction figure of luminescent material, X-coordinate represents diffraction angle scale, and ordinate zou represents intensity scale.
Fig. 4 is Cu (I) complex luminescent material [Cu (QBO) (PPh3)
2] PF
6infrared spectrogram, X-coordinate represents wavelength, and ordinate zou represents transmitance.
Fig. 5 is Cu (I) complex luminescent material [Cu (QBO) (PPh3)
2] PF
6ultravioletvisible absorption light collection of illustrative plates, X-coordinate represents wavelength, and ordinate zou represents absorbancy.
Fig. 6 is Cu (I) complex luminescent material [Cu (QBO) (PPh3)
2] PF
6exciting light collection of illustrative plates, supervisory wavelength is 600nm, has maximum excitation peak at 440nm place; X-coordinate is wavelength, and ordinate zou is intensity.
Fig. 7 is Cu (I) complex luminescent material [Cu (QBO) (PPh3)
2] PF
6utilizing emitted light collection of illustrative plates, excitation wavelength is 440nm, and maximum emission peak is positioned at 600nm place; X-coordinate is wavelength, and ordinate zou is intensity.
Fig. 8 is Cu (I) complex luminescent material [Cu (QBO) (PPh3)
2] PF
6thermal gravimetric analysis curve, X-coordinate represents temperature, and ordinate zou represents weight percentage (left side) and thermal change (right side) respectively.
Embodiment
The present invention is a kind of orange smooth Cu (I) complex luminescent material based on benzoxazolyl quinoline part and preparation method thereof, specify that wherein title complex [Cu (QBO) (PPh3)
2] PF
6molecular structure and steric bulk mode, and the luminescent properties of material and thermostability.Embodiment is as follows:
Embodiment 1
Cuprous complex luminescent material [Cu (QBO) (PPh3)
2] PF
6preparation:
A. Cu (the CH of 0.2mmol is taken
3cN)
4pF
6, be placed in Erlenmeyer flask, add 10mL methylene dichloride, stir, obtain colorless cleared solution 1;
B. take the QBO of 0.2mmol with mantoquita stoichiometric ratio 1: 1, be placed in 10mL beaker, add 5mL methylene dichloride, stir and make it to become yellow clear solution 2;
C. take the PPh3 of 0.4mmol with mantoquita stoichiometric ratio 1: 2, be placed in 10mL beaker, add 5mL methylene dichloride and stir, obtain settled solution solution 3;
D. by solution 2,3 pour in solution 1 successively, stir 1h, by gained solution evaporate to dryness at 40 DEG C, dry, obtain the orange-yellow microcrystal powder of product.
Embodiment 2
Cuprous complex luminescent material [Cu (QBO) (PPh3)
2] PF
6the acquisition of monocrystalline and sign:
The acquisition of monocrystalline adopts interface diffusion process, takes [Cu (QBO) (PPh3) of 0.1mmol
2] PF
6powder, be dissolved in the methylene dichloride of 2mL, be placed in the test tube of 5mL, on solution, cover Virahol again impel product crystallization, sealing, leaves standstill a couple of days, obtains yellow transparent bulk crystals, select a size be 0.42 × 0.38 × 0.32mm single crystal be used for X-ray single crystal diffraction, resolve obtain [Cu (QBO) (PPh3)
2] PF
6molecular structure.The molecular structure of this compound is illustrated in accompanying drawing 1.
To complex luminescent material [Cu (QBO) (PPh3)
2] PF
6pure phase crystal powder sample carried out a series of performance test.TG and DSC test shows that this material has good thermostability, sees accompanying drawing 8.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 light, and chromaticity coordinates value is (0.5485,0.4461), concrete excitation spectrum and emmission spectrum are as shown in accompanying drawing 6 and accompanying drawing 7.Visible, this material can be applicable to the orange-yellow phosphor material that multi-wavelength excites, and is also suitable for very much the orange-yellow phosphor material of OEL luminescent layer.
Claims (3)
1. based on the orange-yellow luminescent material of cuprous title complex of benzoxazolyl quinoline part, it is characterized in that: the structural formula of luminescent material is [Cu (QBO) (PPh
3)
2] PF
6, by Cu (CH
3cN)
4pF
6carry out coordination reaction with part 2-(2-benzoxazole) quinoline and ligand triphenylphosphine to obtain, wherein 2-(2-benzoxazole) quinoline QBO part is the combination of benzoxazole and quinoline, and its molecular structure is such as formula (I):
The molecular structural formula of described complex luminescent material is [Cu (QBO) (PPh
3)
2] PF
6, ion centered by the univalent copper ion in formula, form coordinate bond with two nitrogen-atoms on the phosphorus on triphenylphosphine ligand and 2-(2-benzoxazole) quinoline, its molecular structure is such as formula (II):
Under room temperature, this complex luminescent material is oblique system, P2
1/ c (No.14) spacer, unit cell parameters is
α=90 °, β=989.732 (3) °, γ=90 °,
z=4, D
c=1.4013g/cm
3, monocrystalline is yellow block transparent crystals; This luminescent material structure shows as ionic complex, and wherein hexafluoro-phosphate radical is counter anion, and positively charged ion is then by cuprous ion and part QBO, PPh
3the coordination cation that complexing is formed; Coordination cation is the tetrahedral structure formed by a univalent copper ion and two atom N and two phosphorus atom coordinations.
2. the preparation method of the orange-yellow luminescent material of Cu (I) title complex 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, triphenylphosphine is dissolved in methylene dichloride, obtains colorless cleared solution;
(3) under room temperature, 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 evaporate to dryness under 40 degree, 100 degree lower dry, obtains crystalline orange product powder.
3. the application of Cu according to claim 1 (I) complex luminescent material, it is characterized in that described luminescent material has maximum emission peak at 600nm 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829636B (en) * | 2015-05-21 | 2017-03-08 | 中国计量学院 | A kind of cuprous complex luminescent material of yellow phosphorescence three-fold coordination cationic |
| CN104910896B (en) * | 2015-06-17 | 2017-01-04 | 中国计量学院 | A kind of cuprous orange red phosphor material of coordination compound based on benzoxazolyl group quinoline |
| CN104962281B (en) * | 2015-06-17 | 2017-02-15 | 中国计量学院 | Benzoxazolyl based CuN2P2 orange phosphorescent material |
| CN104946246A (en) * | 2015-07-02 | 2015-09-30 | 浙江理工大学 | Yellow green phosphorescent cuprous complex luminous material based on diphenyleneimine |
| CN104946247A (en) * | 2015-07-02 | 2015-09-30 | 浙江理工大学 | Orange-yellow light-emitting materials of CuIN2P tetrahedron coordination geometry cuprous coordination compound |
| CN104946245A (en) * | 2015-07-02 | 2015-09-30 | 浙江理工大学 | CuBrN2P type cuprous complex yellow phosphorescent material based on diphenyleneimine |
| CN105924469A (en) * | 2016-04-18 | 2016-09-07 | 中国计量大学 | Crystalline benzimidazolyl quinoline cuprous complex luminescent material |
| CN105837604A (en) * | 2016-04-18 | 2016-08-10 | 中国计量大学 | Benzoxazolyl isoquinoline cuprous complex orange red phosphorescent material in crystal form |
| CN105713022A (en) * | 2016-04-18 | 2016-06-29 | 中国计量大学 | Benzimidazolyl quinoline cuprous complex orange phosphorescent material |
| CN105837626A (en) * | 2016-04-18 | 2016-08-10 | 中国计量大学 | Benzoxazolyl isoquinoline cuprous complex orange phosphorescent material |
| CN105884829A (en) * | 2016-05-05 | 2016-08-24 | 中国计量大学 | CuIN2P cuprous complex light-emitting material based on benzoxazolyl pyridine |
| CN105859752A (en) * | 2016-05-05 | 2016-08-17 | 中国计量大学 | Benzoxazole pyridine-based copper iodide complex orange luminous material |
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| CN102558247A (en) * | 2011-12-29 | 2012-07-11 | 南京工业大学 | 4-phosphino-1, 5-naphthyridine derivative copper complex luminescent material and application |
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