CN104927842B - A kind of cuprous complex red luminescent material of CuIN2P type - Google Patents
A kind of cuprous complex red luminescent material of CuIN2P type Download PDFInfo
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Abstract
The invention discloses a kind of red phosphorescent cuprous complex luminescent material of CuIN2P type and preparation method thereof.The phosphorescent complexes of the present invention, carried out complexation reaction by Hydro-Giene (Water Science). and part to obtain, its molecular structural formula is CuI (2 PBO) (TXP 2,5), 2 PBO and TXP 2 in formula, 5 are respectively electric neutrality part 2 (2 benzothiazole) pyridine and three (2,5 xylyl) phosphine.Described coordination compound had both possessed little molecule and had been easily purified the advantage high with luminous efficiency, and had the advantage that easy-to-use organic solvent dissolves.This material is that direct hybrid reaction obtains with the solution of part by Hydro-Giene (Water Science)., has that simple process, equipment is simple, raw material is easy to get and low cost and other advantages.This material can be as luminescence generated by light red light material, it is possible to as the luminescent layer phosphor material in the electroluminescent device of multilamellar organic material composition.
Description
Technical field
The present invention relates to luminescent material technical field, relate to embedded photoluminescent material field and electroluminescent material field, special
Do not relate to field of organic electroluminescent materials.
Background technology
Luminescent material includes luminescence generated by light and the big class application of electroluminescent two.Luminescence generated by light refers to that object is subject to the external world
The irradiation of light source, thus obtain energy and produce the phenomenon exciting and being finally directed at luminescence.Ultraviolet radiation, visible ray and infra-red radiation
Deng all causing luminescence generated by light.Embedded photoluminescent material can be used for fluorescence analysis, traffic signs, tracking and monitoring, agricultural light conversion film,
The aspects such as the scintillator in nuclear detection technology, the fluorescence optical collector in solar energy switch technology.Electroluminescent
(electroluminescent is called for short EL), refer to that luminescent material, under electric field action, is excited by electric current and electric field and sends out
The phenomenon of light, is a kind of luminescence process that electric energy is converted directly into luminous energy.There is the material of this performance, can be fabricated to automatically controlled
Luminescent device, such as light emitting diode (LED) and Organic Light Emitting Diode (Organic Light-Emitting Diode, letter
Claim OLED).And the big series products of LED and OLED two, all have in advanced flat pannel display and solid-state energy-saving illumination field and lure very much
The application prospect of people, and had shown that its good industrialized development impetus at present.
Electroluminescent solid material can be produced and have a variety of, mainly include inorganic semiconductor material, organic molecule
Material, macromolecular material and coordination compound small molecule material.Owing to OLED has energy-conservation, frivolous, free from glare, without ultraviolet, nothing
Infrared ray, driving voltage are low, response time is short, low-temperature characteristics is good, luminous efficiency is high, manufacturing process is simple, all solid state shock resistance
Good, almost without visible angle problem, can manufacture on the substrate of unlike material, can to make the product that can bend etc. numerous
Advantage, enjoys attracting attention of scientific and technological circle and industrial circle in recent years.And along with the development of society, OLED technology is color in (or will)
The fields such as the display terminal of electricity, mobile phone, various display, various illumination use or the military equipment such as decorative lamp, aircraft obtain
Use the most widely.
The operation principle of OLED is under the effect of extra electric field, and hole and electronics are respectively from positive and negative electrode infusion appliance
Part, is compounded to form exciton at luminescent layer, luminous by the attenuation of exciton.And according to spin statistics principle, singlet excitons and
Triplet exciton respectively accounts for 25% and 75%, so utilizing merely the luminescent layer that fluorescent material makes, and will be at most only with 25%
Input energy, other major part energy then can bring serious heating effect, not only the waste energy and also be unfavorable for device
Long-time stable works.Different from the fluorescent material only with singlet excitons energy, transient metal complex phosphor material
Owing to having the strongest SO coupling effect, all input energy including triplet and triplet can be made full use of,
25% energy existed in fundamentally breaching a very long time limits, and the efficiency of OLED is greatly improved, also
That is, utilize transient metal complex phosphor material that the internal quantum of OLED can be made to reach 100%.Therefore exist
In luminescent material based on OLED research, the research and development of phosphor material are particularly important.
More specifically being analyzed, with Ir, the precious metals complex such as Pt, Ru, Re, Os and organic compound are new as one
The luminescent material of type and by extensive concern.OLED phosphor material the most on sale is all the coordination compound of precious metal iridium and platinum etc.,
Although they are existing preferably performance in performance, but these transition metal are expensive, and content is low, exploitation difficulty, certain model
They large-scale application in real life, production are limited in enclosing.Therefore, novel cheap metal combination is found
Object light sulfate ferroelectric functional material just seems extremely important.For noble metal, copper has inexpensively, environmental protection, the advantage such as nontoxic, and
China's copper resource reserve enriches, and occupies third place in the world.Therefore, research based on univalent copper complex luminescence new material, have non-
The most important theory significance and actual application value.The most long-standing as phosphor material with Cu (I) coordination compound
(N.Armaroli, G.Accorsi, F.Cardinali, A.Listorti, Top.Curr.Chem.2007,280,69-115.),
This cheap Cu (I) complex luminescent material can be prepared easily by Cu (I) ion and suitable organic ligand.Cu's (I)
Part, can be monodentate, bidentate or multiple tooth, rigidity or flexibility.There is changeable coordination mode, various selectable ligancy.
There is the structure of monokaryon, double-core or even multinuclear in its space structure simultaneously, and common monokaryon is with 3, and 4 coordinations are main, form triangle
Or positive tetrahedron type, multinuclear can form square such as four cores.The most at present at OLED operating temperature range Cu (I) coordination compound phosphorus
The luminous intensity of luminescent material does not still reach application demand.Therefore develop novel cheap Cu (I) complex phosphorescence material and there is weight
Big actual application value.
Summary of the invention
It is an object of the invention to provide a kind of new red phosphorescent cuprous complex luminescent material of CuIN2P type and preparation thereof
Method.By the solution complexation reaction of Hydro-Giene (Water Science). and organic ligand, convenient and to have prepared luminescent properties at a low price good
The tetrahedral coordination cuprous complex luminescent material of CuIN2P type, its red phosphorescent luminous intensity is very big, heat stability might as well, and
And its decay of luminescence feature meets the OLED requirement to material phosphorescence luminescent lifetime very much, it is applied to OLED luminescent layer
Material is conducive to the reduction of product cost.
One of technical scheme, is to provide a kind of new red phosphorescent CuIN2P type cuprous coordination compound luminescence material
Material, is carried out complexation reaction by Hydro-Giene (Water Science). and part and obtains, and its molecular structural formula is CuI (2-PBO) (TXP-2,5), 2-in formula
PBO and TXP-2,5 be respectively the most electroneutral containing P part three (2,5-xylyl) phosphine with heterocyclic ligand 2-(2-benzothiazole) pyrrole
Pyridine.
Described part 2-(2-benzothiazole) pyridine, is the coalition of benzothiazole and pyridine, its molecular structure such as formula
(I):
In described part, a N in benzoxazoles structure and an atom N on pyridine ring are formed double with cuprous ion
The coordination mode of tooth chelating.
Described luminescent material is rhombic system, Pbca space group, cell parameter α=90 °, β=90 °, γ=90 °,Z=8, Dc=1.462g/cm3, crystal color
For yellow, profile is block；Coordination compound shows as the electroneutral tetrahedral coordination cuprous coordination compound of CuIN2P type, Cu therein
(I) CuIN is used2P tetrahedral four-coordination pattern, two N are respectively from the pyrrole in the 2-PBO part of a bidentate chelating
Piperidinyl group and benzothiazole group, a P comes from an end group TXP-2,5 parts；The molecular structure of described luminescent material is such as
Formula (II):
Described luminescent material is applied to red light phosphor material, and this material is by the widest wave-length coverage (300-550nm)
Exciting of ultraviolet light or visible ray, can send the strongest red light, and its maximum emission wavelength is 620nm, and chromaticity coordinates value is
(0.6247,0.3749), luminescent lifetime is 4 microseconds.
Described red phosphorescent luminescent material is used as the luminescent layer phosphorescence in the electroluminescent device of multilamellar organic material composition
Material.
The two of technical scheme, are to provide a kind of red phosphorescent CuIN2P type cuprous complex luminescent material CuI
(2-PBO) preparation method of (TXP-2,5).This preparation method is that after being mixed with the solution of part by Hydro-Giene (Water Science)., generation coordination is anti-
Should, then solvent is removed thus separate out the crystal of product and realize.Its specific embodiments is divided into five steps:
(1) under room temperature, the powder of Hydro-Giene (Water Science). is completely dissolved in acetonitrile；
(2) under room temperature, the powder of part three (2,5-xylyl) phosphine is dissolved completely in dichloromethane；
(3) the two solution is mixed, and stirring is allowed to fully occur complexation reaction to obtain solution A；
(4) toward solution A adds the acetonitrile solution of 2-PBO, and stir and be allowed to fully occur complexation reaction；
(5) reactant liquor is steamed at vacuumized conditions backspin, remove solvent and i.e. obtain the fine crystals product of yellow.
In the preparation method of the present invention, mol ratio CuI of described three kinds of reactants: 2-PBO: TXP-2,5 is 1: 1: 1.
First beneficial effects of the present invention is provided red phosphorescent CuIN2P type cuprous complex luminescent material CuI
(2-PBO) (TXP-2,5), wherein the existence of halogen iodine can change the excited state composition of molecule so that the electricity of Ni metal to part
Lotus transition (MLCT) excited state adds the biggest halogen charge transtion composition to part, and new (X+M) CT excited state is not
It is only capable of effectively facilitating intersystem crossing and can effectively suppress the non-radiative decay of excited state；And on the other hand methyl is contained in adjacency pair position
Phosphine ligands three (2,5-xylyl) phosphine to cause Cu (I) around to exist bigger sterically hindered, cooperation can be stablized well
The tetrahedral coordination configuration of thing molecule, thus the non-radiative decay of Inhibitory molecules excited state, thus what this molecular material had had
Phosphorescent emissions performance.This complex material had both possessed advantage that is cheap and that be prone to purification, and had good dissolubility, heat surely
Qualitative, the application further for luminescent material provides technical support.
Beneficial effects of the present invention, next to that prepare red phosphorescent CuIN2P type cuprous complex luminescent material CuI (2-
PBO) method of (TXP-2,5), has simple process, and device therefor is simple, and raw material is simple and easy to get, and production cost is low, Ke Yi
The advantages such as the product with very high yield are obtained in the shortest time.
Accompanying drawing explanation
Fig. 1. the mono-crystalline structures figure of phosphorescent complexes CuI (2-PBO) (TXP-2,5).
Fig. 2. phosphorescent complexes CuI (2-PBO) (TXP-2,5) is in unit cell and peripheral space accumulation graph.
Fig. 3. the X-ray powder diffraction spectrum of phosphorescent complexes CuI (2-PBO) (TXP-2,5): (a) is according to embodiment
In 2, single crystal structural data calculates the spectrogram obtained；B () is the collection of illustrative plates of gained powder in the embodiment of the present invention 1.
Fig. 4. the Fourier transform infrared light collection of illustrative plates of phosphorescent complexes CuI (2-PBO) (TXP-2,5), abscissa table
Oscillography number, vertical coordinate represents transmitance.
Fig. 5. the thermal gravimetric analysis curve of phosphorescent complexes CuI (2-PBO) (TXP-2,5), abscissa represents temperature, vertical coordinate
Represent percetage by weight.
Fig. 6. ultraviolet-ray visible absorbing (UV-Vis) spectrogram of phosphorescent complexes CuI (2-PBO) (TXP-2,5).
Fig. 7. the excitation spectrum that coordination compound CuI (2-PBO) (TXP-2,5) crystallite sample measures under 620 nanometer supervisory wavelength
Figure.
Fig. 8. coordination compound CuI (2-PBO) (TXP-2,5) crystallite sample light emission spectrum under 420 nano wave length light excite
Figure.
Detailed description of the invention
The process that realizes of the present invention and the performance of material are illustrated by embodiment:
Embodiment 1
The preparation of substantial amounts of crystallite sample: the CuI weighing 0.5mmol is dissolved in 10mL acetonitrile, weigh 0.5 three (2,
5-xylyl) Phosphine ligands is dissolved in the dichloromethane of 8mL, is mixed by both solution, and stirring is allowed to fully join
Position reaction obtains colourless solution A；Then the 2-PBO part weighing 0.5mmol is dissolved in 8mL acetonitrile, is then added by this solution
Enter in above-mentioned solution A, and stirring is allowed to fully occur complexation reaction, is finally evaporated off all molten by the rotation of gained yellow reaction liquid
Agent, vacuum drying, obtain yellow crystalline powder and be product, productivity 97% (in terms of Cu).
Embodiment 2
The monocrystalline of synthesis phosphorescence cuprous coordination compound CuI (2-PBO) (TXP-2,5): the CuI weighing 0.1mmol is dissolved in 3mL
In acetonitrile, weigh three (2,5-xylyl) Phosphine ligands of 0.1 and be dissolved in the dichloromethane of 3mL, both solution is mixed,
And stirring is allowed to fully occur complexation reaction to obtain colourless solution A；Then the 2-PBO part weighing 0.1mmol is dissolved in 2mL second
In nitrile, then this solution is added in above-mentioned solution A, and stirring is allowed to fully occur complexation reaction, finally by molten for gained yellow
Liquid filters, and covers normal hexane and promotes product to crystallize, separate out a large amount of yellow bulk crystals after standing a couple of days on filtrate.Select one
The yellow bulk transparent crystal of 0.38mm × 0.30mm × 0.23mm size is used for X-ray single crystal diffraction structured testing.This chemical combination
The molecular structure of thing is shown graphically in the attached figures 1, and its structure cell packed structures is illustrated in accompanying drawing 2.
The pure phase crystal prototype of coordination compound CuI (2-PBO) (TXP-2,5) cuprous to phosphorescence has carried out a series of performance and has surveyed
Examination.Thermogravimetric (TG) test shows that this material has preferable stability, as shown in Figure 5.Material crystals of the present invention has been carried out surely
State fluorometric investigation, result shows that this material, under different excitation wavelength effects, can launch strong red light, chromaticity coordinates
Value is (0.6247,0.3749), and concrete excitation spectrum and emission spectrum are as shown in accompanying drawing 7 and accompanying drawing 8.And the wink to this material
State fluorometric investigation shows, its luminescent lifetime is 4 microseconds, belongs to phosphorescent emissions.Visible, this material can be applicable to multi-wavelength and excites
Red phosphorescence material, be also very suitable for the red light phosphor material for OLED luminescent layer.
Claims (4)
1. the red phosphorescent cuprous complex luminescent material of CuIN2P type, it is characterised in that: the structural formula of luminescent material is CuI
(2-PBO) (TXP-2,5), TXP-2 in formula, 5 contain P part three (2,5-xylyl) phosphine for electric neutrality；During in formula, 2-PBO is electricity
Property heterocyclic ligand 2-(2-benzothiazole) pyridine, this part is the coalition of benzothiazole and pyridine, its molecular structure such as formula
(I):
Described luminescent material is rhombic system, Pbca space group, cell parameter α=90 °, β=90 °, γ=90 °,Z=8, Dc=1.462g/cm3, crystal color is yellow, and profile is
Block；Coordination compound shows as the electroneutral tetrahedral coordination cuprous coordination compound of CuIN2P type, and Cu therein (I) uses CuIN2P tetra-
Face build four-coordination pattern, two N are respectively from the pyridine groups in the 2-PBO part of a bidentate chelating and benzothiazole
Group, a P comes from an end group TXP-2,5 parts；The molecular structure of described luminescent material such as formula (II):
The preparation method of the cuprous complex luminescent material of red phosphorescent CuIN2P type, the method bag the most according to claim 1
Include following steps:
(1) under room temperature, the powder of Hydro-Giene (Water Science). is completely dissolved in acetonitrile；
(2) under room temperature, the powder of part three (2,5-xylyl) phosphine is dissolved completely in dichloromethane；
(3) the two solution is mixed, and stirring is allowed to fully occur complexation reaction to obtain solution A；
(4) toward solution A adds the acetonitrile solution of 2-PBO, and stir and be allowed to fully occur complexation reaction；
(5) reactant liquor is steamed at vacuumized conditions backspin, remove solvent and i.e. obtain the fine crystals product of yellow；Three kinds of reactants
Mol ratio CuI: 2-PBO: TXP-2,5 is 1: 1: 1.
The application of the cuprous complex luminescent material of red phosphorescent CuIN2P type the most according to claim 1, it is characterised in that institute
State luminescent material and be used as red light embedded photoluminescent material.
The application of the cuprous complex luminescent material of red phosphorescent CuIN2P type the most according to claim 1, it is characterised in that institute
State the luminescent layer phosphor material that luminescent material is used as in the electroluminescent device of multilamellar organic material composition.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105713021A (en) * | 2016-04-18 | 2016-06-29 | 中国计量大学 | Methyl-substituted benzoxazolyl pyridine cuprous complex yellow/green phosphorescent material |
| 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 |
| CN105884829A (en) * | 2016-05-05 | 2016-08-24 | 中国计量大学 | CuIN2P cuprous complex light-emitting material based on benzoxazolyl pyridine |
| 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 |
| CN105859752A (en) * | 2016-05-05 | 2016-08-17 | 中国计量大学 | Benzoxazole pyridine-based copper iodide complex orange luminous material |
| CN106085413B (en) * | 2016-07-04 | 2018-08-24 | 湖北工业大学 | A kind of narrow emission hybrid inorganic-organic red light material and preparation method thereof |
| CN110372733B (en) * | 2019-08-21 | 2021-12-14 | 郑州大学 | Metal organic copper complex with fluorescent property and preparation method thereof |
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 (1)
| Title |
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| Structures, electronic properties and solid state luminescence of Cu(I) iodide complexes with 2,9-dimethyl-1,10-phenanthroline and aliphatic aminomethylphosphines or triphenylphosphine;Radosław Starosta等;《Dalton Transaction》;20110201(第40期);2459-2468 * |
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