CN108794514A - A kind of cuprous complex orange phosphor material of Xantphos and PBO mixed matchings - Google Patents
A kind of cuprous complex orange phosphor material of Xantphos and PBO mixed matchings Download PDFInfo
- Publication number
- CN108794514A CN108794514A CN201710310491.3A CN201710310491A CN108794514A CN 108794514 A CN108794514 A CN 108794514A CN 201710310491 A CN201710310491 A CN 201710310491A CN 108794514 A CN108794514 A CN 108794514A
- Authority
- CN
- China
- Prior art keywords
- xantphos
- ligand
- pbo
- complex
- cuprous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- CXNIUSPIQKWYAI-UHFFFAOYSA-N xantphos Chemical compound C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 58
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003446 ligand Substances 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 12
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 8
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 230000003760 hair shine Effects 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims 1
- 239000011368 organic material Substances 0.000 abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 32
- 238000010668 complexation reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000011365 complex material Substances 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- -1 iridium (Ir) Chemical class 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
-
- 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
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention discloses a kind of cuprous complex orange phosphor materials and preparation method thereof based on biphosphine ligand and 3- (2- benzoxazoles) pyridine ligand of crystal form.The phosphorescent complexes of the present invention, are obtained by cuprous salt and ligand complex, and molecular structure is [Cu (Xantphos) (3-PBO)2](PF6), Xantphos is electroneutral biphosphine ligand 4 in formula, and bis- diphenylphosphine -9, the 9- xanthphos of 5-, 3-PBO is heterocyclic ligand 3- (2- benzoxazoles) pyridine.The complex had both had small molecule and has been easily purified the advantage high with luminous efficiency, and had high thermal stability.The material is by Cu (CH3CN)4PF6It is obtained with the direct hybrid reaction of dichloromethane solution of ligand, has many advantages, such as that simple process, equipment be simple, raw material is easy to get and at low cost.The material can be used as luminescence generated by light orange light phosphor material, 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 fields, are 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
The development of information technology makes people, and to the display technology as information system outlet terminal, more stringent requirements are proposed.
It shows that (PDP) etc. is modern with traditional cathode-ray display technology (CRT) and liquid crystal display (LCD), plasma and shows skill
Art is compared, and organic electroluminescence device (OLED) has the advantages that a lot of other devices are incomparable, becomes 21 century optical telecommunications
One of the advanced subject to attract attention in the development of breath technology, has obtained extensively and in-depth study.And luminescent material is Organic Electricity
Core in electroluminescence device.
Organic electroluminescent abbreviation OEL is to have electric energy to excite organic material and luminous phenomenon, early in the sixties in last century
It just has been observed that, but widely pays attention to without causing due to lacking clear application prospect.1987, Eastern Kodak were public
Tang of department et al. has made operating voltage low (about 10V), brightness height (more than 1000cd/m2), the efficient double-deck Organic Electricity
Electroluminescence device, just make organic electroluminescent really gone on rapid development road (Applied Physics Letters,
1987,51,913-915.).Nineteen ninety Cambridge University is developed based on the OLED new technologies of macromolecule luminous organic material.1994
Year, the Chuner Mitsumasa etc. of Japanese chevron university invented white luminous device, and so that the application of organic electroluminescence device is become can
Energy.Mouth this pioneer electronics in 1997 is proposed the OLED products automobile audio display screen one by one of the first in the world commercialization, steps
The first step of OLED industrialization.Industry is even more the upsurge for having started and having invested and developing to OLED since especially 2000,
Commercially, the fields such as industry, communication, traffic, computer have been shown up prominently.OLED is that one kind is formed by multilayer organic thin film structure
Electroluminescent device, have the advantages that other display devices are incomparable：1. operating condition：Driving voltage is low, low in energy consumption,
OLED is not necessarily to back lighting, and power consumption of driver is small；2. in terms of display：It actively shines, angular field of view is big, image stabilization, brightness
Height, rich in color, high resolution；3. design aspect：It is simple in structure, it is at low cost, background light source and optical filter are not needed, can be manufactured
The product for going out ultra-thin, light weight, being easy to carry about with one；4. wide adaptability：It can realize that large-area flat-plate is shown using glass substrate, use is soft
Property material does substrate, and folding display can be made；5. environmental suitability is strong：It, can be in low temperature with good temperature characterisitic
Display etc. under environment.
In order to prepare the OLED device of high-luminous-efficiency, by the further investigation in more than 30 years, various new electricity is had been developed that
The performance of electroluminescent material, prepared device is also significantly increased.People synthesize and have studied a large amount of transient metal complex,
Such as iridium (Ir), golden (Au), platinum (Pt) etc..Up to the present, the OLED based on phosphorescence Ir complexs maintains highest shine
Efficiency.But iridium content in nature is very low and expensive, seriously hinder its commercialization progress, so introduce it is low at
This phosphorescent metal complex, such as cuprous complex.China's copper resource is abundant, and copper ore resource just has at 910, gross reserves 6234
Ten thousand tonnages occupy the world the 7th.There is apparent advantage for those transition metal elements, and the price of copper is cheap, nontoxic
And it is small to environmental pressure.In addition to this, the coordination mode of Cu (I) complex is very abundant, can be former with 2,3,4 coordinations respectively
Son coordination forms linear type, plane trigonometry type, the mononuclear complex of tetrahedral structure and one-dimensional, two-dimentional, three-dimensional etc. without knot
The polynuclear complex of structure, abundant chemical constitution cause it with unique Photophysics.Therefore, it is based on univalent copper complex
The research of luminous new material, has very important theory significance and actual application value.And because it is in optical physics and photochemistry
The outstanding behaviours of aspect, application of the cuprous complex material in electroluminescent field are increasingly subject to China and foreign countries scientist and relevant industry
The attention of personage.
Most of high efficiency Cu (I) the complexs OLED reported at present are mainly green emission, how to develop high efficiency orange/
Yellow light Cu (I) complex OLED urgently to be resolved hurrily this need to utilize chemical synthesis means exploitation high-luminous-efficiency, different luminescent colors
Cu (I) complex.Secondly, the stability of Cu (I) complex needs further to be studied.Although preliminary result of study shows Cu
(I) complex has stability more better than Ir complex, but more detailed, in-depth study is to investigate cheap Cu (I) cooperation
Whether OLE can be in the premise of display and lighting area application.
Invention content
The purpose of the content of present invention is to provide a kind of cuprous complex luminescent material of orange phosphor and preparation method thereof.Pass through
Complexation reaction occurs for the solution of cuprous ion and ligand, convenient and inexpensively prepared luminescent properties and thermal stability is good
Good cuprous complex luminescent material, orange phosphor luminous intensity is big, thermal stability is good, and its decay of luminescence characteristic is very
Meet requirement of the OLED device to material phosphorescence luminescent lifetime, is applied to OLED emitting layer materials and is conducive to product cost drop
It is low.
One of technical scheme of the present invention is to provide a kind of cuprous complex luminescent material of new orange phosphor, by Cu
(CH3CN)4PF6Complexation reaction occurs successively with ligand to obtain, molecular structure is [Cu (Xantphos) (3-PBO)2](PF6),
Xantphos is electroneutral biphosphine ligand 4 in formula, and bis- diphenylphosphine -9, the 9- xanthphos of 5-, 3-PBO is heterocyclic ligand 3-
(2- benzoxazoles) pyridine.
The luminescent material is anorthic system, and P-1 space groups, cell parameter is α=82.381 (2) °, β=80.043 (2) °, γ=83.130 (2) °,Z=2, DC
=1.292g/cm3, the crystal color of material is yellow；The luminescent material structure shows as ionic complex, wherein hexafluoro phosphorus
Acid group is counter anion, and cation be then by cuprous ion and ligand 3-PBO, Xantphos be complexed the coordination sun formed from
Son；Cuprous ion uses CuN in the complex cation2P2Tetrahedral coordination mode, two of which N are respectively from two
Pyridine groups in nitrogen ligand 3-PBO, two P come from the Phosphine ligands Xantphos of bidentate chelating；Its molecular structure is such as
Formula (I)：
The luminescent material be applied to orange phosphor material, the material by very wide wave-length coverage (400-550nm) purple
The excitation of outer light or visible light can send out very strong orange-colored light, and unimodal feature is presented in luminescent spectrum, and peak emission wavelength is
585nm, chromaticity coordinates are (0.4238,0.4510), and luminescent lifetime is 1.1 microseconds.
The two of technical scheme of the present invention are to provide a kind of cuprous complex luminescent material [Cu of orange phosphor
(Xantphos)(3-PBO)2](PF6) preparation method.The preparation method is by Cu (CH3CN)4PF6With ligand 3-PBO and
Complexation reaction occurs for the dichloromethane solution mixing of Xantphos, is finally precipitated and obtains the product of crystal powder and realize.It has
Body embodiment is divided into five steps：
(1) at room temperature by Cu (CH3CN)4PF6Powder dissolves in methylene chloride；
(2) Xantphos powder is dissolved in methylene chloride at room temperature；
(3) two kinds of solution mixing are stated by described, and stirs and is allowed to fully react, obtain clear solution A；
(4) 3-PBO powder is dissolved in methylene chloride at room temperature, adds in solution A and be mixed, is allowed to fully send out
Raw complexation reaction obtains solution B；
(5) acquired solution B is subjected to vacuum rotary steam at room temperature, be dried in vacuo, obtained yellow crystals are the material that shines
Expect product；Molar ratio Cu (the CH of above-mentioned three kinds of reactants3CN)4PF6: Xantphos: 3-PBO 1: 1: 2.
Beneficial effects of the present invention are the cuprous complex luminescent material [Cu of provided mixed matching orange phosphor first
(Xantphos)(3-PBO)2](PF6), it shines wherein the benzoxazole group introduced is conducive to molecular-excited state, Ni metal is to matching
The presence of the charge transtion (MLCT) of body effectively facilitates intersystem crossing, and the presence of the groups such as a large amount of phenyl ring and bidentate chelate
Big steric hindrance biphosphine ligand Xantphos presence, cause Cu (I) surrounding ligands there are effective steric hindrance, can inhibit molecule and swash
The non-radiative decay of state is sent out, ligand 3-PBO and Xantphos are the ligand of more aromatic rings, all have prodigious rigidity characteristic, because
And the phosphorescent emissions performance that the molecular material has had.The advantages of complex material had both had inexpensively and had been easy to purifying, and
With good dissolubility and thermal stability, technical support is provided for the further application of luminescent material.
Beneficial effects of the present invention followed by prepare the cuprous complex luminescent material [Cu of mixed matching orange phosphor
(Xantphos)(3-PBO)2](PF6) method, have simple process, device therefor is simple, and production cost is low, can be very short
Time in obtain the product with very high yield.
Description of the drawings
Fig. 1 phosphorescent complexes material [Cu (Xantphos) (3-PBO)2](PF6) molecule mono-crystalline structures figure.
Fig. 2 phosphorescent complexes material [Cu (Xantphos) (3-PBO)2](PF6) molecule is in unit cell and its peripheral space
Accumulation graph.
Fig. 3 phosphorescent complexes material [Cu (Xantphos) (3-PBO)2](PF6) X-ray powder diffraction collection：(a)
For the collection of illustrative plates of gained powder in the embodiment of the present invention 1；(b) it is that the spectrogram obtained is calculated according to single crystal structural data in embodiment 2.
Fig. 4 phosphorescent complexes material [Cu (Xantphos) (3-PBO)2](PF6) ultraviolet-ray visible absorbing (UV-Vis) light
Spectrogram
Fig. 5 phosphorescent complexes material [Cu (Xantphos) (3-PBO)2](PF6) crystal prototype 360 nano wave length light swash
Give the light emitting spectrogram of measurement.
Fig. 6 phosphorescent complexes material [Cu (Xantphos) (3-PBO)2](PF6) crystal prototype 470 nano wave length light swash
Give the light emitting spectrogram of measurement.
Fig. 7 phosphorescent complexes material [Cu (Xantphos) (3-PBO)2](PF6) crystal prototype is in 585 nanometers of supervisory wavelengths
The excitation spectrogram of lower measurement.
Specific implementation mode
The realization process of the present invention and the performance of material are illustrated by embodiment：
Embodiment 1
A large amount of phosphorescent complexes material [Cu (Xantphos) (3-PBO)2](PF6) crystal prototype preparation：It weighs
Cu (the CH of 0.037g (0.1mmol)3CN)4PF6, the Xantphos of 0.058g (0.1mmol), the 3- of 0.039g (0.2mmol)
PBO；It is mixed successively after being dissolved respectively with the dichloromethane of 5ml, is sufficiently stirred and is allowed to that complexation reaction fully occurs, obtain orange-yellow
Clear solution；By above-mentioned solution, vacuum rotary steam removes all solvents at room temperature, finally obtains yellow crystals product, yield is
90% (being calculated with Cu).
Embodiment 2
Synthesize orange phosphor complex material [Cu (Xantphos) (3-PBO)2](PF6) monocrystalline：Weigh 0.037g
Cu (the CH of (0.1mmol)3CN)4PF6, the Xantphos of 0.058g (0.1mmol), the 3-PBO of 0.039g (0.2mmol)；Respectively
With being mixed successively after the dissolving of the dichloromethane of 5ml, it is sufficiently stirred and is allowed to that complexation reaction fully occurs, it is molten to obtain orange-yellow clarification
Liquid；After filtering, on solution upper layer, covering n-hexane promotes product to crystallize, and has a large amount of yellow needle-like crystals to be precipitated after several days standing.
The yellow needle-like crystals for selecting a 0.50mm*0.06mm*0.06mm size are tested for x-ray crystal structure.The compound
Molecular structure be shown graphically in the attached figures 1, structure cell packed structures are illustrated in attached drawing 2.
To orange phosphor complex material [Cu (Xantphos) (3-PBO)2](PF6) pure phase crystal prototype carried out one
A little row performance tests.Steady-state fluorescence test is carried out to material crystals of the present invention, the results showed that the material is different and excite
Under wavelength effect, strong orange phosphor can be launched, chromaticity coordinates value is (0.4238,0.4510), specific excitation spectrum
With emission spectrum as shown in attached drawing 5, attached drawing 6 and attached drawing 7.And its luminescent lifetime, which is, to be shown to the transient state fluorometric investigation of the material
1.1 microseconds, belong to phosphorescent emissions.As it can be seen that the material can be applied to the orange phosphor material of multi-wavelength's excitation, it is also very suitable for
Orange phosphor material for OLED luminescent layers.
Claims (3)
1. a kind of cuprous complex of orange phosphor based on biphosphine ligand and 3- (2- benzoxazoles) pyridine ligand of crystal form shines
Material, it is characterised in that：The structural formula of luminescent material is [Cu (Xantphos) (3-PBO)2](PF6), Xantphos is electricity in formula
Neutral biphosphine ligand 4, bis- diphenylphosphine -9, the 9- xanthphos of 5-, 3-PBO are Nitrogen-Containing Heterocyclic Ligand 3- (2- benzoxazoles)
Pyridine；Above-mentioned complex phosphorescence material is anorthic system, and P-1 space groups, cell parameter is α=82.381 (2) °, β=80.043 (2) °, γ=83.130 (2) °,Z=2, Dc=
1.292g/cm3, the crystal color of material is yellow；The luminescent material structure shows as ionic complex, wherein hexafluorophosphoric acid
Root is counter anion, and cation be then by cuprous ion and ligand 3-PBO, Xantphos be complexed the coordination sun formed from
Son；Cuprous ion uses CuN in the complex cation2P2Tetrahedral coordination mode, two of which N are respectively from two
Pyridine groups in nitrogen ligand 3-PBO, two P come from the Phosphine ligands Xantphos of bidentate chelating；Its molecular structure is such as
Formula (I)：
2. the preparation method of cuprous complex orange phosphor material, method include the following steps according to claim 1：
(1) at room temperature by Cu (CH3CN)4PF6Powder dissolves in methylene chloride；
(2) Xantphos powder is dissolved in methylene chloride at room temperature；
(3) above two solution is mixed, and stirs and is allowed to fully react, obtain clear solution A；
(4) 3-PBO powder is dissolved in methylene chloride at room temperature, adds in solution A and be mixed, is allowed to fully match
React to obtain solution B in position；
(5) acquired solution B is subjected to vacuum rotary steam at room temperature, be dried in vacuo, obtained yellow crystals are luminescent material production
Object；Molar ratio Cu (the CH of above-mentioned three kinds of reactants3CN)4PF6: Xantphos: 3-PBO 1: 1: 2.
3. the application of cuprous complex orange phosphor material according to claim 1, it is characterised in that the luminescent material
Unimodal feature is presented in luminescent spectrum, and peak emission wavelength 585nm can be used as orange light transmitting embedded photoluminescent material, or as more
Luminescent layer luminescent material in layer electroluminescent device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710310491.3A CN108794514A (en) | 2017-04-28 | 2017-04-28 | A kind of cuprous complex orange phosphor material of Xantphos and PBO mixed matchings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710310491.3A CN108794514A (en) | 2017-04-28 | 2017-04-28 | A kind of cuprous complex orange phosphor material of Xantphos and PBO mixed matchings |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108794514A true CN108794514A (en) | 2018-11-13 |
Family
ID=64054651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710310491.3A Pending CN108794514A (en) | 2017-04-28 | 2017-04-28 | A kind of cuprous complex orange phosphor material of Xantphos and PBO mixed matchings |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108794514A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591365A (en) * | 2022-03-22 | 2022-06-07 | 郑州大学 | Light-emitting copper compound based on benzimidazole phosphine oxide ligand and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910896A (en) * | 2015-06-17 | 2015-09-16 | 中国计量学院 | Cuprous complex orange red phosphorescent material based on benzoxazolyl quinoline |
| CN104961770A (en) * | 2015-06-17 | 2015-10-07 | 中国计量学院 | Pyronyl phosphine ligand based cuprous-complex green phosphorescent material |
| CN105694868A (en) * | 2016-04-18 | 2016-06-22 | 中国计量大学 | Benzimidazolyl-quinoline cuprous complex light-emitting material |
-
2017
- 2017-04-28 CN CN201710310491.3A patent/CN108794514A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910896A (en) * | 2015-06-17 | 2015-09-16 | 中国计量学院 | Cuprous complex orange red phosphorescent material based on benzoxazolyl quinoline |
| CN104961770A (en) * | 2015-06-17 | 2015-10-07 | 中国计量学院 | Pyronyl phosphine ligand based cuprous-complex green phosphorescent material |
| CN105694868A (en) * | 2016-04-18 | 2016-06-22 | 中国计量大学 | Benzimidazolyl-quinoline cuprous complex light-emitting material |
Non-Patent Citations (2)
| Title |
|---|
| PASCAL LE FLOCH等: "Biphosphinine-copper(I) complexes: chelate vs.polymeric helical structures", 《BULLETIN DE LA SOCIETE CHIMIQUE DE FRANCE》 * |
| YAN-RU ZHANG等: "Syntheses, structural characterizations and terahertz spectra of Ag(I)/Cu(I) complexes with bis[2-(diphenylphosphino)phenyl]ether and N^N ligands", 《POLYHEDRON》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591365A (en) * | 2022-03-22 | 2022-06-07 | 郑州大学 | Light-emitting copper compound based on benzimidazole phosphine oxide ligand and preparation method and application thereof |
| CN114591365B (en) * | 2022-03-22 | 2023-09-05 | 郑州大学 | Luminous copper compound based on benzimidazole phosphine oxide ligand and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104910896B (en) | A kind of cuprous orange red phosphor material of coordination compound based on benzoxazolyl group quinoline | |
| CN103833777B (en) | A kind of cuprous complex luminescent material based on benzoxazolyl quinoline part | |
| CN106459095A (en) | Metal organic framework (MOF) yellow phosphors and their applications in white light emitting devices | |
| CN105924469A (en) | Crystalline benzimidazolyl quinoline cuprous complex luminescent material | |
| CN104140808A (en) | Tetrahedral cuprous complex luminescent material containing oxazolyl pyridine ligands | |
| CN103880867A (en) | Di-nuclear cuprous complex green luminescent material and preparation method thereof | |
| CN104961770B (en) | A kind of cuprous complex green phosphorescent material based on pyridine radicals phosphine part | |
| CN103626789A (en) | Binuclear cuprous complex luminescent material and preparation method thereof | |
| CN104178131B (en) | A kind of cuprous complex luminescent material of mixed matching of Han oxazolyl pyridine ligand | |
| CN104861962B (en) | A kind of Cu4I4 class cubane bunch core complex luminescent material based on Phosphine ligands | |
| CN105694868B (en) | Benzimidazolyl-quinoline cuprous complex light-emitting material | |
| CN104893715B (en) | Copper iodide phosphorescent complex light-emitting material containing Cu4I4 cluster core | |
| CN108794513A (en) | A kind of cuprous complex luminescent material of green phosphorescent of double phosphines and pyridines mixture | |
| CN105884829A (en) | CuIN2P cuprous complex light-emitting material based on benzoxazolyl pyridine | |
| CN104962281B (en) | Benzoxazolyl based CuN2P2 orange phosphorescent material | |
| CN105837626A (en) | Benzoxazolyl isoquinoline cuprous complex orange phosphorescent material | |
| CN108794514A (en) | A kind of cuprous complex orange phosphor material of Xantphos and PBO mixed matchings | |
| CN106967117A (en) | A kind of cuprous complex yellow phosphorescence luminescent materials of BINAP | |
| CN105713022A (en) | Benzimidazolyl quinoline cuprous complex orange phosphorescent material | |
| CN103865523A (en) | Double-core cuprous iodide complex luminescent material | |
| CN105754591B (en) | A kind of crystal formation of the cuprous complex luminescent material of benzoxazolyl isoquinolin | |
| CN106008562A (en) | Tetrahedral cuprous complex luminescent material containing phenanthroline ligand | |
| CN108794534A (en) | A kind of cuprous complex orange phosphor luminescent material of BINAP and PBO mixtures | |
| CN105837604A (en) | Benzoxazolyl isoquinoline cuprous complex orange red phosphorescent material in crystal form | |
| CN106967121A (en) | A kind of cuprous complex yellow phosphorescence luminescent material of 8 hydroxyl quinaldines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181113 |