CN105838356B - A kind of cuprous complex orange light emitting materials of CuBrN2P types based on benzoxazole yl pyridines - Google Patents
A kind of cuprous complex orange light emitting materials of CuBrN2P types based on benzoxazole yl pyridines Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 69
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 150000003222 pyridines Chemical class 0.000 title abstract description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 23
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010668 complexation reaction Methods 0.000 claims abstract description 11
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000011368 organic material Substances 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000004020 luminiscence type Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000003384 small molecules Chemical class 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 230000005284 excitation Effects 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000005684 electric field Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000001052 transient effect Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 0 *[Cn](*1C=CCCC11)(*(c2ccccc2)(c2ccccc2)c2ccccc2)*2c1[o]c1c2cccc1 Chemical compound *[Cn](*1C=CCCC11)(*(c2ccccc2)(c2ccccc2)c2ccccc2)*2c1[o]c1c2cccc1 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
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- C—CHEMISTRY; METALLURGY
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
The invention discloses a kind of cuprous complex luminescent material of orange phosphor CuBrN2P types based on benzoxazole yl pyridines and preparation method thereof.The phosphorescent complexes of the present invention, carry out complexation reaction with part by cuprous bromide and obtain, its molecular structural formula is CuBr (2 PBO) (PPh3), 2 PBO and PPh in formula3Respectively (2 benzoxazole) pyridine of electroneutral part 2 and triphenylphosphine.The complex both possessed small molecule be easily purified with luminous efficiency it is high the advantages of, and with easy-to-use organic solvent dissolving the advantages of.The material is obtained by the direct hybrid reaction of solution of cuprous bromide and part, has simple process, equipment is simple, raw material is easy to get and low cost and other advantages.The material can be used as the orange luminescent material of luminescence generated by light, it is also possible to make the luminescent layer phosphor material in the electroluminescent device of multilayer organic material composition.
Description
Technical field
The present invention relates to luminescent material technical field, is related to embedded photoluminescent material field and electroluminescent material field, special
It is not to be related to field of organic electroluminescent materials.
Background technology
Luminescent material includes luminescence generated by light and the major class application field of electroluminescent two.Luminescence generated by light refers to object by the external world
The irradiation of light source, excite so as to obtain energy production and be finally directed at luminous phenomenon.Ultraviolet radioactive, visible ray and infra-red radiation
Deng can cause luminescence generated by light.Embedded photoluminescent material can be used for fluorescence analysis, traffic sign, tracking and monitoring, agricultural light conversion film,
Fluorescence optical collector in scintillator, solar energy switch technology in nuclear detection technology etc..Electroluminescent
(electroluminescent, abbreviation EL), refer to that luminescent material under electric field action, is excited and sent out by electric current and electric field
The phenomenon of light, it is a kind of luminescence process that electric energy is converted directly into luminous energy.Material with this performance, it 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 LED and the major class products of OLED two, all have in advanced FPD and solid-state energy-saving illumination field and lure very much
The application prospect of people, and its good industrialized development impetus has been had shown that at present.
Electroluminescent solid material, which can be produced, many kinds, mainly including inorganic semiconductor material, organic molecule
Material, high polymer material and complex small molecule material.Because OLED has energy-conservation, frivolous, free from glare, without ultraviolet, nothing
Infrared ray, driving voltage are low, the response time is short, low-temperature characteristics is good, luminous efficiency is high, manufacturing process is simple, all solid state shock resistance
It is good, almost there is no the problem of visible angle, can be manufactured on the substrate of unlike material, can to make the product that can be bent etc. numerous
Advantage, attracting attention for scientific and technological circle and industrial circle is enjoyed in recent years.And with the development of society, OLED technology is color (or will)
Electricity, mobile phone, various displays, various illuminations with or the field such as the display terminal of military equipment such as decorative lamp, aircraft obtain
More and more extensive use.
The operation principle of OLED is in the presence of extra electric field, and hole and electronics are respectively from positive and negative electrode injector
Part, exciton is compounded to form in luminescent layer, is lighted by the attenuation of exciton.And according to spin statistics principle, singlet excitons and
Triplet exciton respectively accounts for 25% and 75%, so the luminescent layer made using fluorescent material merely, will can only at most utilize 25%
Input energy, other most of energy can then bring serious heating effect, not only waste the energy but also are unfavorable for device
Long-time stable works.It is different from the fluorescent material of singlet excitons energy can only be utilized, transient metal complex phosphor material
Due to being acted on very strong SO coupling, all input energies including triplet and triplet can be made full use of,
Existing 25% energy limitation in a very long time is fundamentally breached, the efficiency of OLED is greatly improved,
That is the internal quantum that can make OLED using transient metal complex phosphor material reaches 100%.Therefore exist
In luminescent material research based on OLED, the research and development of phosphor material are particularly important.
More specifically analyzed, with the precious metals complex such as Ir, Pt, Ru, Re, Os and organic compound as a kind of new
The luminescent material of type and by extensive concern.OLED phosphor materials on sale at present are all the complexs of precious metal iridium and platinum etc.,
Although their existing preferably performances in performance, these transition metal are expensive, and content is low, and exploitation is difficult, certain model
Their large-scale applications in real life, production are limited in enclosing.Therefore, new cheap metal combination is found
Object light sulfate ferroelectric functional material just seems extremely important.For noble metal, copper has the advantage such as cheap, environmentally friendly, nontoxic, and
China's copper resource rich reserves, occupy third place in the world.Therefore, lighted the research of new material based on univalent copper complex, is had non-
Often important theory significance and actual application value.It is and then long-standing by the use of Cu (I) complexs as phosphor material
(N.Armaroli, G.Accorsi, F.Cardinali, A.Listorti, Top.Curr.Chem.2007,280,69-115.),
This cheap Cu (I) complex luminescent material can easily be prepared by Cu (I) ions and suitable organic ligand.Cu's (I)
Part, can be monodentate, bidentate or multiple tooth, rigidity or flexible.With changeable coordination mode, various selectable ligancy.
Simultaneously there is the structure of monokaryon, double-core or even multinuclear in its space structure, and common monokaryon forms triangle based on 3,4 coordinations
Or positive tetrahedron type, multinuclear can form square such as four cores.Simply at present in OLED operating temperature ranges Cu (I) complex phosphorus
The luminous intensity of luminescent material does not reach application demand still.Therefore developing new cheap Cu (I) complex phosphorescences material has weight
Big actual application value.
The content of the invention
It is an object of the invention to provide a kind of new cuprous complex luminescent material of orange phosphor CuBrN2P types and its preparation
Method.It is convenient and inexpensively to have prepared luminescent properties good by the solution complexation reaction of cuprous bromide and organic ligand
The cuprous complex luminescent material of tetrahedral coordination CuBrN2P types, its orange phosphor luminous intensity is very big, heat endurance might as well,
And its decay of luminescence feature meets requirement of the OLED to material phosphorescence luminescent lifetime very much, is applied to OLED and lights
Layer material is advantageous to the reduction of product cost.
One of technical scheme, it is to provide a kind of luminous material of new cuprous complex of orange phosphor CuBrN2P types
Material, carry out complexation reaction with part by cuprous bromide and obtain, its molecular structural formula is CuBr (2-PBO) (PPh3), 2-PBO in formula
And PPh3Respectively heterocyclic ligand 2- (2- benzoxazoles) pyridines of electroneutral and ligand triphenylphosphine containing P.
Part 2- (2- benzoxazoles) pyridine, is the combination of benzoxazole and pyridine, its molecular structure such as formula (I)：
A N atom on a N and pyridine ring in the part in benzoxazoles structure forms double with cuprous ion
The coordination mode of tooth chelating.
The luminescent material is monoclinic system, P21/ c space groups, cell parameter α=90 °, β=103.330 (6) °, γ=90 °,Z=4, Dc=1.509g/
cm3, crystal color is yellow, and profile is bulk；Complex shows as the cuprous cooperation of tetrahedral coordination CuBrN2P types of electroneutral
Thing, Cu (I) therein use CuBrN2P tetrahedral four-coordination patterns, two N are respectively from the 2- of a bidentate chelating
Pyridine groups and benzoxazole group in PBO parts, a P come from an end group part PPh3；The luminescent material
Molecular structure such as formula (II)：
The luminescent material is applied to orange-colored light phosphor material, and the material is by very wide wave-length coverage (300-500nm)
Exciting for ultraviolet light or visible ray, can send very strong orange-colored light, its maximum emission wavelength is 645nm, and chromaticity coordinates value is
(0.5701,0.4289), luminescent lifetime are 6.2 microseconds.
The orange phosphor luminescent material is used as the luminescent layer phosphorescence in the electroluminescent device of multilayer organic material composition
Material.
The two of technical scheme, it is to provide a kind of cuprous complex luminescent material of orange phosphor CuBrN2P types
CuBr(2-PBO)(PPh3) preparation method.The preparation method is coordinated after being mixed by cuprous bromide with the solution of part
Reaction, then solvent is removed and realized so as to separate out the crystal of product.Its specific embodiment is divided into five steps：
(1) powder of cuprous bromide is completely dissolved in acetonitrile at room temperature；
(2) powder of ligand triphenylphosphine is dissolved completely in dichloromethane at room temperature；
(3) described two solution are mixed, and stirs and be allowed to complexation reaction fully occurs to obtain solution A；
(4) toward the acetonitrile solution of addition 2-PBO in solution A, and stir and be allowed to that complexation reaction fully occurs；
(5) reaction solution is rotated under vacuumized conditions, removes solvent and obtain the fine crystals product of yellow.
In the preparation method of the present invention, mol ratio CuBr: 2-PBO: PPh of three kinds of reactants3For 1: 1: 1.
Beneficial effects of the present invention are the provided cuprous complex luminescent material CuBr of orange phosphor CuBrN2P types first
(2-PBO)(PPh3), the wherein presence of halogen bromine can change the excitation state composition of molecule so that the electric charge jump of Ni metal to part
The charge transtion composition that very big halogen is added in (MLCT) excitation state to part is moved, and new (X+M) CT excitation state can not only
Effectively facilitate intersystem crossing and can effectively suppress the non-radiative decay of excitation state；And the Phosphine ligands three that another aspect volume is larger
Phenylphosphine causes larger steric hindrance be present around Cu (I), can stable complex molecule well tetrahedral coordination structure
Type, so as to suppress the non-radiative decay of molecular-excited state, thus the phosphorescent emissions performance that the molecular material has had.The complex
The advantages of material had both possessed inexpensively and had been easy to purifying, and with good dissolubility, heat endurance, for luminescent material
Further application provides technical support.
Beneficial effects of the present invention, next to that preparing the cuprous complex luminescent material CuBr (2- of orange phosphor CuBrN2P types
PBO)(PPh3) method, there is simple process, device therefor is simple, and raw material is simple and easy to get, and production cost is low, can be very short
Time in obtain having the advantages that the product of very high yield.
Brief description of the drawings
Fig. 1 phosphorescent complexes CuBr (2-PBO) (PPh3) mono-crystalline structures figure.
Fig. 2 phosphorescent complexes CuBr (2-PBO) (PPh3) in unit cell and its peripheral space accumulation graph.
Fig. 3 phosphorescent complexes CuBr (2-PBO) (PPh3) ultraviolet-ray visible absorbing (UV-Vis) spectrogram.
Fig. 4 complexs CuBr (2-PBO) (PPh3) crystal prototype determined under 645 nanometers of supervisory wavelengths excite spectrogram.
Fig. 5 complexs CuBr (2-PBO) (PPh3) light emission spectrum figure of the crystal prototype in the case where 410 nano wave length light excite.
Embodiment
The implementation process of the present invention and the performance of material are illustrated by embodiment：
Embodiment 1
The preparation of substantial amounts of crystallite sample：The CuBr for weighing 0.5mmol is dissolved in 10mL acetonitriles, weighs 0.5 triphen
Base Phosphine ligands are dissolved in 8mL dichloromethane, and both solution are mixed, and are stirred and be allowed to complexation reaction fully occurs to obtain
Colourless solution A；Then the 2-PBO parts for weighing 0.5mmol are dissolved in 8mL acetonitriles, and this solution then is added into above-mentioned solution A
In, and stir and be allowed to that complexation reaction fully occurs, gained yellow reaction liquid revolving is finally removed into all solvents, is dried in vacuo,
It is product to obtain orange-yellow crystal powder, yield 96% (in terms of Cu).
Embodiment 2
Synthesize cuprous complex CuBr (the 2-PBO) (PPh of phosphorescence3) monocrystalline：The CuBr for weighing 0.1mmol is dissolved in 5mL
In acetonitrile, weigh 0.1 triphenylphosphine ligand and be dissolved in 4mL dichloromethane, both solution are mixed, and stir and be allowed to
Complexation reaction fully occurs and obtains colourless solution A；Then the 2-PBO parts for weighing 0.1mmol are dissolved in 2mL acetonitriles, then
This solution is added in above-mentioned solution A, and stirs and is allowed to that complexation reaction fully occurs, finally filters gained yellow solution,
N-hexane is covered on filtrate promotes product to crystallize, and a large amount of yellow bulk crystals are separated out after standing a couple of days.Select a 0.32mm ×
The yellow bulk transparent crystal of 0.29mm × 0.23mm sizes is used for X-ray single crystal diffraction structured testing.The molecule of the compound
Structure chart is shown graphically in the attached figures 1, and its structure cell packed structures is illustrated in accompanying drawing 2.
Complex CuBr (2-PBO) (PPh cuprous to phosphorescence3) pure phase crystal prototype carried out a series of performance tests.
Steady-state fluorescence test is carried out to material crystals of the present invention, the results showed that the material, can under different excitation wavelength effects
Launch strong orange-colored light, chromaticity coordinates value is (0.5701,0.4289), specific excitation spectrum and emission spectrum such as accompanying drawing 4
Shown in accompanying drawing 5.And the transient state fluorometric investigation of the material is shown, its luminescent lifetime is 6.2 microseconds, belongs to phosphorescent emissions.Can
See, the material can be applied to the orange phosphor material that multi-wavelength excites, and be also very suitable for the orange-colored light for OLED luminescent layers
Phosphor material.
Claims (4)
- A kind of 1. cuprous complex luminescent material of orange phosphor CuBrN2P types, it is characterised in that：The structural formula of luminescent material is CuBr(2-PBO)(PPh3), PPh in formula3For electroneutral ligand triphenylphosphine containing P；2-PBO is electroneutral heterocyclic ligand 2- in formula (2- benzoxazoles) pyridine, the part are the combinations of benzoxazole and pyridine, its molecular structure such as formula (I)：The luminescent material is monoclinic system, P21/ c space groups, cell parameter α=90 °, β=103.330 (6) °, γ=90 °,Z=4, Dc=1.509g/cm3, crystal color is Huang Color, profile are bulk；Complex shows as the cuprous complex of tetrahedral coordination CuBrN2P types of electroneutral, and Cu (I) therein is adopted Use CuBrN2P tetrahedral four-coordination patterns, two N are respectively from the pyridine radicals in the 2-PBO parts of a bidentate chelating Group and benzoxazole group, a P come from an end group part PPh3；The molecular structure of the luminescent material such as formula (II)：
- 2. the preparation method of the cuprous complex luminescent material of orange phosphor CuBrN2P types according to claim 1, this method bag Include following steps：(1) powder of cuprous bromide is completely dissolved in acetonitrile at room temperature；(2) powder of ligand triphenylphosphine is dissolved completely in dichloromethane at room temperature；(3) above two solution is mixed, and stirs and be allowed to complexation reaction fully occurs to obtain solution A；(4) toward the acetonitrile solution of addition 2-PBO in solution A, and stir and be allowed to that complexation reaction fully occurs；(5) reaction solution is rotated under vacuumized conditions, removes solvent and obtain the fine crystals product of yellow；Three kinds of reactants Mol ratio CuBr: 2-PBO: PPh3For 1: 1: 1.
- 3. the application of the cuprous complex luminescent material of orange phosphor CuBrN2P types according to claim 1, it is characterised in that institute State luminescent material and be used as orange-colored light embedded photoluminescent material.
- 4. the application of the cuprous complex luminescent material of orange phosphor CuBrN2P types according to claim 1, it is characterised in that institute State the luminescent layer phosphor material in electroluminescent device of the luminescent material as multilayer organic material composition.
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| CN201610307169.0A CN105838356B (en) | 2016-05-05 | 2016-05-05 | A kind of cuprous complex orange light emitting materials of CuBrN2P types based on benzoxazole yl pyridines |
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| CN105838356B true CN105838356B (en) | 2018-03-02 |
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| CN103588794A (en) * | 2013-11-22 | 2014-02-19 | 中国计量学院 | Cuprous complex luminescence material and preparation method thereof |
| CN103626789A (en) * | 2013-11-22 | 2014-03-12 | 中国计量学院 | Binuclear cuprous complex luminescent material and preparation method thereof |
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| CN103588794A (en) * | 2013-11-22 | 2014-02-19 | 中国计量学院 | Cuprous complex luminescence material and preparation method thereof |
| CN103626789A (en) * | 2013-11-22 | 2014-03-12 | 中国计量学院 | Binuclear cuprous complex luminescent material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Mixed-ligand complexes of copper(I) with diimines and phosphines:Effective catalysts for the coupling of phenylacetylene with halobenzene;Fazal, Atif等;《Polyhedron》;20091208;第28卷(第18期);4072-4076 * |
| Structures, electronic properties and solid state luminescence of Cu(I) iodide complexes with 2,9-dimethyl-1,10-phenanthroline and aliphatic aminomethylphosphines or triphenylphosphine;Rados等;《dalton transction》;20110201;2459-2468 * |
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