CN105838356A - CuBrN2P type cuprous complex orange luminescent material based on benzoxazolyl pyridine - Google Patents
CuBrN2P type cuprous complex orange luminescent material based on benzoxazolyl pyridine Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 72
- WELSCYIRWKBEBZ-UHFFFAOYSA-N 2-pyridin-2-yl-1,3-benzoxazole Chemical compound N1=CC=CC=C1C1=NC2=CC=CC=C2O1 WELSCYIRWKBEBZ-UHFFFAOYSA-N 0.000 title abstract 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 24
- 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 23
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 8
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims abstract description 7
- 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 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000010668 complexation reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 abstract 2
- 230000000536 complexating effect Effects 0.000 abstract 1
- 238000005401 electroluminescence Methods 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 238000005424 photoluminescence Methods 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 10
- 238000004020 luminiscence type Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 230000005281 excited state 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
- 230000000694 effects Effects 0.000 description 3
- 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
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000005286 illumination Methods 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
- 230000005855 radiation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 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
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 230000015572 biosynthetic process 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
- -1 compound small molecule Chemical class 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 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
- 238000001802 infusion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-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
- 238000000746 purification Methods 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 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
-
- 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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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Engineering & Computer Science (AREA)
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- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a CuBrN2P type cuprous complex orange luminescent material based on benzoxazolyl pyridine and a preparing method of the CuBrN2P type cuprous complex orange luminescent material. A phosphorescence complex is obtained through a complexing reaction of cuprous bromide and a ligand, and the molecular structural formula of the phosphorescence complex is CuBr(2-PBO)(PPh3), wherein 2-PBO and PPh3 in the formula are an electric neutral ligand 2-(2-benzoxazole)pyridine and triphenylphosphine respectively. The complex has the advantages of being easy to purify due to small molecules and high in luminescent efficiency, and has the advantage of being easy to dissolve with an organic solvent. The material is obtained through a reaction achieved by directly mixing cuprous bromide and a ligand solution, and has the advantages that the process is easy and convenient, equipment is simple, raw materials are easy to obtain, and cost is low. The material can serve as a photoluminescence orange light material and can also serve as a luminescent layer phosphorescent material in an electroluminescence device composed of multiple layers of organic materials.
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 orange phosphor cuprous complex luminescent material of CuBrN2P type and preparation thereof
Method.By the solution complexation reaction of cuprous bromide and organic ligand, convenient and to have prepared luminescent properties at a low price good
The tetrahedral coordination cuprous complex luminescent material of CuBrN2P type, its orange phosphor luminous intensity is very big, heat stability might as well,
And its decay of luminescence feature meets the OLED requirement to material phosphorescence luminescent lifetime very much, it is applied to OLED luminous
Layer material is conducive to the reduction of product cost.
One of technical scheme, is to provide a kind of new orange phosphor CuBrN2P type cuprous coordination compound luminescence material
Material, is carried out complexation reaction by cuprous bromide and part and obtains, and its molecular structural formula is CuBr (2-PBO) (PPh3), 2-PBO in formula
And PPh3It is respectively electroneutral heterocyclic ligand 2-(2-benzothiazole) pyridine and the ligand triphenylphosphine Han P.
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 monoclinic system, P21/ c space group, cell parameter α=90 °, β=103.330 (6) °, γ=90 °,Z=4, Dc=1.509g/
cm3, crystal color is yellow, and profile is block；Coordination compound shows as the electroneutral tetrahedral coordination cuprous cooperation of CuBrN2P type
Thing, Cu therein (I) uses CuBrN2P tetrahedral four-coordination pattern, two N are respectively from the 2-of a bidentate chelating
Pyridine groups in PBO part and benzothiazole group, a P comes from an end group part PPh3；Described luminescent material
Molecular structure such as formula (II):
Described luminescent material is applied to orange-colored light phosphor material, and this material is by the widest wave-length coverage (300-500nm)
Exciting of ultraviolet light or visible ray, can send the strongest orange-colored light, and its maximum emission wavelength is 645nm, and chromaticity coordinates value is
(0.5701,0.4289), luminescent lifetime is 6.2 microseconds.
Described orange phosphor 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 orange phosphor cuprous complex luminescent material of CuBrN2P type
CuBr(2-PBO)(PPh3) preparation method.This preparation method be mixed with the solution of part by cuprous bromide after be coordinated
Reaction, then removes solvent thus separates out the crystal of product and realize.Its specific embodiments is divided into five steps:
(1) under room temperature, the powder of cuprous bromide is completely dissolved in acetonitrile；
(2) under room temperature, the powder of ligand triphenylphosphine 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 CuBr of described three kinds of reactants: 2-PBO: PPh3It is 1: 1: 1.
First beneficial effects of the present invention is provided orange phosphor CuBrN2P type cuprous complex luminescent material CuBr
(2-PBO)(PPh3), wherein the existence of halogen bromine can change the excited state composition of molecule so that the electric charge of Ni metal to part jumps
Move and (MLCT) excited state adds the biggest halogen charge transtion composition to part, and new (X+M) CT excited state can not only
Effectively facilitate intersystem crossing and can effectively suppress the non-radiative decay of excited state；And the Phosphine ligands three that on the other hand volume is bigger
It is bigger sterically hindered that Phenylphosphine causes Cu (I) around to exist, can the tetrahedral coordination structure of stable complex molecule well
Type, thus the non-radiative decay of Inhibitory molecules excited state, thus the phosphorescent emissions performance that this molecular material has had.This coordination compound
Material had both possessed advantage that is cheap and that be prone to purification, and had good dissolubility, heat stability, for luminescent material
Application provides technical support further.
Beneficial effects of the present invention, next to that prepare orange phosphor CuBrN2P type cuprous complex luminescent material CuBr (2-
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 the shortest
Time in obtain the advantages such as the product with very high yield.
Accompanying drawing explanation
Fig. 1. phosphorescent complexes CuBr (2-PBO) (PPh3) mono-crystalline structures figure.
Fig. 2. phosphorescent complexes CuBr (2-PBO) (PPh3) in unit cell and peripheral space accumulation graph.
Fig. 3. phosphorescent complexes CuBr (2-PBO) (PPh3) ultraviolet-ray visible absorbing (UV-Vis) spectrogram.
Fig. 4. coordination compound CuBr (2-PBO) (PPh3) crystal prototype measure under 645 nanometer supervisory wavelength excite spectrogram.
Fig. 5. coordination compound CuBr (2-PBO) (PPh3) crystal prototype light emission spectrogram under 410 nano wave length light excite.
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 CuBr weighing 0.5mmol is dissolved in 10mL acetonitrile, weighs the triphen of 0.5
Base Phosphine ligands is dissolved in the dichloromethane of 8mL, is mixed by both solution, and stirring is allowed to fully occur complexation reaction to obtain
Colourless solution A；Then the 2-PBO part weighing 0.5mmol is dissolved in 8mL acetonitrile, then this solution is added above-mentioned solution A
In, and stir and be allowed to fully occur complexation reaction, finally the rotation of gained yellow reaction liquid is evaporated off all solvents, vacuum drying,
Obtain orange-yellow crystal powder and be product, productivity 96% (in terms of Cu).
Embodiment 2
Synthesis phosphorescence cuprous coordination compound CuBr (2-PBO) (PPh3) monocrystalline: the CuBr weighing 0.1mmol is dissolved in 5mL
In acetonitrile, weigh the triphenylphosphine ligand of 0.1 and be dissolved in the dichloromethane of 4mL, both solution is mixed, and stir and be allowed to
Complexation reaction is fully occurred to obtain colourless solution A；Then the 2-PBO part weighing 0.1mmol is dissolved in 2mL acetonitrile, then
This solution is added in above-mentioned solution A, and stirring is allowed to fully occur complexation reaction, is finally filtered by gained yellow solution,
Covering normal hexane on filtrate promotes product to crystallize, and separates out a large amount of yellow bulk crystals after standing a couple of days.Select a 0.32mm ×
The yellow bulk transparent crystal of 0.29mm × 0.23mm size is used for X-ray single crystal diffraction structured testing.The molecule of this compound
Structure chart is shown graphically in the attached figures 1, and its structure cell packed structures is illustrated in accompanying drawing 2.
Coordination compound CuBr (2-PBO) (PPh cuprous to phosphorescence3) pure phase crystal prototype carried out a series of performance test.
Material crystals of the present invention has been carried out steady-state fluorescence test, and result shows that this material, can under different excitation wavelength effects
Launching strong orange-colored light, chromaticity coordinates value is (0.5701,0.4289), concrete excitation spectrum and emission spectrum such as accompanying drawing 4
Shown in accompanying drawing 5.And the transient state fluorometric investigation of this material is shown, its luminescent lifetime is 6.2 microseconds, belongs to phosphorescent emissions.Can
Seeing, this material can be applicable to the orange phosphor material that multi-wavelength excites, and is also very suitable for the orange-colored light for OLED luminescent layer
Phosphor material.
Claims (5)
1. the orange phosphor cuprous complex luminescent material of CuBrN2P type, it is characterised in that: the structural formula of luminescent material is
CuBr(2-PBO)(PPh3), PPh in formula3For electric neutrality ligand triphenylphosphine Han P；In formula, 2-PBO is electric neutrality 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 monoclinic system, P21/ c space group, cell parameter α=90 °, β=103.330 (6) °, γ=90 °,Z=4, Dc=1.509g/cm3, crystal color is yellow
Color, profile is block；Coordination compound shows as the electroneutral tetrahedral coordination cuprous coordination compound of CuBrN2P type, and Cu therein (I) adopts
Use CuBrN2P tetrahedral four-coordination pattern, two N are respectively from the pyridine radicals in the 2-PBO part of a bidentate chelating
Group and benzothiazole group, a P comes from an end group part PPh3；The molecular structure of described luminescent material such as formula (II):
The preparation method of the cuprous complex luminescent material of orange phosphor CuBrN2P type, the method bag the most according to claim 1
Include following steps:
(1) under room temperature, the powder of cuprous bromide is completely dissolved in acetonitrile；
(2) under room temperature, the powder of ligand triphenylphosphine 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.
The most according to claim 2, the preparation method of the cuprous complex luminescent material of orange phosphor CuBrN2P type, its feature exists
In: mol ratio CuBr of described three kinds of reactants: 2-PBO: PPh3It is 1: 1: 1.
The application of the cuprous complex luminescent material of orange phosphor CuBrN2P type the most according to claim 1, it is characterised in that institute
State luminescent material and be used as orange-colored light embedded photoluminescent material.
The application of the cuprous complex luminescent material of orange phosphor CuBrN2P 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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| CN107011888A (en) * | 2017-03-21 | 2017-08-04 | 中国计量大学 | A kind of cuprous complex luminescent material of the tetrahedral containing phenanthroline ligand of crystal formation |
| CN109776614A (en) * | 2019-03-25 | 2019-05-21 | 中国计量大学 | A kind of cuprous complex fluorescent sensing material of pair of 4- picoline steam selective response |
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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 |
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| FAZAL, ATIF等: "Mixed-ligand complexes of copper(I) with diimines and phosphines:Effective catalysts for the coupling of phenylacetylene with halobenzene", 《POLYHEDRON》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011888A (en) * | 2017-03-21 | 2017-08-04 | 中国计量大学 | A kind of cuprous complex luminescent material of the tetrahedral containing phenanthroline ligand of crystal formation |
| CN109776614A (en) * | 2019-03-25 | 2019-05-21 | 中国计量大学 | A kind of cuprous complex fluorescent sensing material of pair of 4- picoline steam selective response |
| CN109776614B (en) * | 2019-03-25 | 2021-03-19 | 中国计量大学 | Cuprous complex fluorescent sensing material selectively responding to 4-methylpyridine steam |
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