CN106008562A - Tetrahedral cuprous complex luminescent material containing phenanthroline ligand - Google Patents
Tetrahedral cuprous complex luminescent material containing phenanthroline ligand Download PDFInfo
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- CN106008562A CN106008562A CN201610307149.3A CN201610307149A CN106008562A CN 106008562 A CN106008562 A CN 106008562A CN 201610307149 A CN201610307149 A CN 201610307149A CN 106008562 A CN106008562 A CN 106008562A
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- 239000000463 material Substances 0.000 title claims abstract description 55
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000003446 ligand Substances 0.000 title claims abstract description 11
- 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 46
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000011368 organic material Substances 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 13
- 238000010668 complexation reaction Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 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
- 239000003960 organic solvent Substances 0.000 abstract 1
- 238000005424 photoluminescence Methods 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
- 238000004020 luminiscence type Methods 0.000 description 7
- 238000011160 research Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- RICKKZXCGCSLIU-UHFFFAOYSA-N 2-[2-[carboxymethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]ethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]acetic acid Chemical compound CC1=NC=C(CO)C(CN(CCN(CC(O)=O)CC=2C(=C(C)N=CC=2CO)O)CC(O)=O)=C1O RICKKZXCGCSLIU-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005286 illumination 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
- -1 iridium (Ir) Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 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
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005395 radioluminescence 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
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000904 thermoluminescence Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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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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- 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
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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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- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- 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
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- 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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- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention discloses a green phosphorescence tetrahedral cuprous complex luminescent material and preparing method thereof. A phosprehorescence complex is obtained through complexing of cuprous salt and a ligand, and the molecular structure of the phosphorescence complex is Cu(Phen)(PPh3)2(PF6), wherein Phen and PPh3 are electric neutrality ligands 1,10-phenanthroline and triphenylphosphine respectively. The complex has the advantages of being easy to purify due to small molecules and high in luminous efficiency, and also has the advantage of being easily dissolved with an organic solvent. The material is obtained through a reaction by directly mixing Cu(CH3CN)4PF6 and solutions of the two ligands, and has the advantages that the technology is easy and convenient to implement, equipment is simple, raw materials are easy to obtain, and cost is low. The material can serve as a photoluminescence green ray material and can also serve as a luminescent layer phosphorescence material in an electroluminescent device composed of multiplayer 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 has luminescence generated by light, cathode-ray luminescence, electroluminescent, thermoluminescence, light to release luminescence, radioluminescence
Deng.Wherein, electroluminescent (electroluminescent, be called for short EL), refer to luminescent material under electric field action, by electric current
With exciting of electric field and the phenomenon of luminescence, also known as electroluminescence.Current electroluminescent research direction is mainly organic material
Application, such as Organic Light Emitting Diode (Organic Light-Emitting Diode is called for short OLED).By its luminescent material
Molecular weight, OLED can be divided into little molecule Organic Light Emitting Diode (OLED or SM-OLED), and macromolecule (also known as polymer) is organic
Light emitting diode (PLED or P-OLED) two class, the former molecular weight between 500～2000, the latter 10000～100000 it
Between.
From reported first such as Tang in 1987 organic electroluminescence device of high brightness and low-work voltage (OLEDs) it
After, everybody has had unprecedented research enthusiasm to it.Take the lead in after OLEDs commercialization, because of it from Japanese Pioneer company in 1997
Huge commercial value in terms of solid-state illumination and display and be considered as the flat panel display of a new generation.OLED is as flat board
Display Technique, compared with existing lcd technology, has faster response speed, lower driving voltage, broader regarding
The distinguishing features such as angle, can be further applied TV, computer, instrument etc. as display screen.Nowadays, Samsung, LG, Sony,
Numerous International Electro major company such as Sharp has participated among the technical research of OLEDs one after another.
Organic electroluminescent can be divided into fluorescence and phosphorescence two class by its luminescence mechanism: the former is that the radiation of singlet excitons declines
Subtracting transition, luminescent lifetime is nanosecond；The latter is caused by triplet exciton attenuation transition, because existing in its transition process
Prohibit, therefore luminescent lifetime is Microsecond grade.If the luminescent layer of device only makes of fluorescent material, can be by its internal quantum efficiency
(IQE) restriction of (in theory only 25%) and the energy can not be made full use of.And transition metal such as iridium (Ir), ruthenium (Ru), rhenium
(Re), the emitting complexes such as platinum (Pt) as a kind of phosphor material because having the strongest SO coupling effect, can be abundant
Utilize all input energy including triplet and triplet, therefore its internal quantum efficiency can reach 100% in theory, compares fluorescence
Material exceeds whole more than three times.The domestic personage being engaged in OLED research is then many using noble metals such as iridium as phosphor.But iridium etc.
Coordination compound presently, there are that cost is high, resource is few and the inevitable limitation such as not environmentally.Therefore, research and develop some low costs,
The phosphor material of multiple resource and environmental protection is extremely urgent.Cu (I) coordination compound is with its environmental protection and cheap etc. advantage is fine appears
Angle, also has the features such as copper resource reserve is big, structure diversification, photophysical property are unique and day by day receives much attention because of it.
Through research and development for many years, find that Cu (I) coordination compound there is also some shortcomings, as Cu (I) joins in reality is used
Compound glow color is much the most high based on green glow and blue light, luminosity.We try to introduce some specific functions
Functional group promotes luminosity and the efficiency of Cu (I) coordination compound.Phen and derivant thereof are widely used in photoelectricity material
The fields such as material, wherein 1, the emitting complexes that 10-Phen is easily stable with cuprous ion coordination formation, such coordination compound has
Good physicochemical properties, therefore be widely used in preparing electroluminescent organic material.Develop novel cheap Cu (I) to coordinate
Thing green phosphorescent material has great actual application value.
Summary of the invention
It is an object of the invention to provide a kind of new cuprous complex luminescent material of green phosphorescent tetrahedral and preparation thereof
Method.By Cu (I) ion and the solution complexation reaction of organic ligand, convenient and to have prepared luminescent properties at a low price good
Cu (I) complex luminescent material, its green phosphorescent luminous intensity is very big, and its decay of luminescence feature meets OLED device very much
The part requirement to material phosphorescence luminescent lifetime, is applied to OLED emitting layer material and is conducive to the reduction of product cost.
One of technical scheme, is to provide a kind of new green phosphorescent tetrahedral cuprous coordination compound luminescence material
Material, by Cu (CH3CN)4PF6Carrying out complexation reaction with part to obtain, its molecular structure is Cu (Phen) (PPh3)2(PF6), in formula
Phen and PPh3It is respectively electric neutrality ligand 1,10-Phen and triphenylphosphine.
Described ligand 1,10-Phen, its molecular structure such as formula (I):
Atom N in described part and cuprous ion form the coordination mode of a bidentate chelating.
Described luminescent material is monoclinic system, P21/ n space group, cell parameter α=90 °, β=92.013 (3) °, γ=90 °,Z=4, Dc=1.429g/cm3, brilliant
Body color is light green color；Coordination compound shows as ionic complex, and counter anion therein is hexafluoro-phosphate radical, and cation
It is then by cuprous ion and part Phen, PPh3The coordination cation that complexation is formed；In this coordination cation, Cu (I) uses
CuN2P2Tetrahedral coordination pattern, two of which N both is from the Phen part of a bidentate chelating, and two P come from two
PPh3Part；Its molecular structure such as formula (II):
Described luminescent material is applied to green glow phosphor material, and this material is by the purple of the widest wave-length coverage (300-470nm)
Exciting of outer light or visible ray, can send the strongest green light, and its maximum emission wavelength is 510nm, and chromaticity coordinates value is
(0.2505,0.5177), luminescent lifetime is 4 microseconds.
Described green phosphorescent luminescent material is used as the luminescent layer phosphorescence in the electroluminescent device of multilamellar organic material composition
Material.
The two of technical scheme, are to provide a kind of green phosphorescent tetrahedral cuprous coordination compound Cu (Phen)
(PPh3)2(PF6) preparation method of luminescent material.This preparation method is by Cu (CH3CN)4PF6With two kinds of parts in the solution
There is complexation reaction in mixing, is then removed by solvent thus separate out the crystal of product and realize.Its specific embodiments is divided into four
Individual step:
(1) by Cu (CH under room temperature3CN)4PF6It is completely dissolved in acetonitrile and dichloromethane mixed solvent；
(2) by part Phen and PPh under room temperature3Powder be dissolved completely in dichloromethane；
(3) the two solution is mixed, and stirring is allowed to fully occur complexation reaction；
(4) by reacting liquid filtering, and gained filtrate is quickly revolved steaming under vacuumized conditions after adding normal hexane, remove molten
Agent i.e. obtains subdiaphanous fine crystals product.
In the preparation method of the present invention, the mol ratio Cu (CH of described three kinds of reactants3CN)4PF6∶Phen∶PPh3It is 1: 1:
2。
First beneficial effects of the present invention is provided green phosphorescent tetrahedral cuprous coordination compound Cu (Phen)
(PPh3)2(PF6) luminescent material, wherein the phenanthroline ligand rigidity of armaticity is very big, is very beneficial for molecular-excited state and sends out
Light, the existence of the charge transtion (MLCT) of Ni metal to part effectively facilitates intersystem crossing, and the biggest Phosphine ligands three
It is bigger sterically hindered that Phenylphosphine causes Cu (I) around to exist, such that it is able to the non-radiative decay of Inhibitory molecules excited state, thus
The phosphorescent emissions performance that this molecular material has had.This complex material had both possessed advantage that is cheap and that be prone to purification, and had
Having good dissolubility, the application further for luminescent material provides technical support.
Beneficial effects of the present invention, next to that preparation green phosphorescent Cu (I) coordination compound Cu (Phen) (PPh3)2(PF6) luminous
The method of material, has simple process, and device therefor is simple, and raw material is simple and easy to get, and production cost is low, can be in the shortest time
Inside obtain the advantages such as the product with very high yield.
Accompanying drawing explanation
Fig. 1. phosphorescent complexes Cu (Phen) (PPh3)2(PF6) the mono-crystalline structures figure of molecule.
Fig. 2. phosphorescent complexes Cu (Phen) (PPh3)2(PF6) molecule is in unit cell and peripheral space accumulation graph.
Fig. 3. phosphorescent complexes Cu (Phen) (PPh3)2(PF6) ultraviolet-ray visible absorbing (UV-Vis) spectrogram.
Fig. 4. phosphorescent complexes Cu (Phen) (PPh3)2(PF6) TG-DTA (TG-DSC) analyze curve, abscissa table
Temp. displaying function, left side vertical coordinate represents that percetage by weight, right side vertical coordinate represent heat.
Fig. 5. coordination compound Cu (Phen) (PPh3)2(PF6) excitation spectrum that measures under 510 nanometer supervisory wavelength of crystal prototype
Figure.
Fig. 6. coordination compound Cu (Phen) (PPh3)2(PF6) crystal prototype light emission spectrum under 430 nano wave length light excite
Figure.
Detailed description of the invention
The process that realizes of the present invention and the performance of material are illustrated by embodiment:
Embodiment 1
Substantial amounts of Cu (Phen) (PPh3)2(PF6) preparation of crystal prototype: first weigh 373mg Cu (CH3CN)4PF6Dissolve
In the dichloromethane mixed solvent of 2mL acetonitrile and 8mL, then weigh the PPh of Phen and 525mg of 198mg3Part dissolves together
In the dichloromethane of 10mL (mol ratio of described three kinds of reactants is 1: 1: 2), both solution is mixed, and stirring is allowed to
Fully there is complexation reaction, finally gained yellow solution is filtered, and quickly rotation is evaporated off all solvents, very after adding normal hexane
Empty dry, obtain pole light green color (the most colourless) crystal powder and be product, productivity 98% (in terms of Cu).
Embodiment 2
Synthesis Cu (I) coordination compound Cu (Phen) (PPh3)2(PF6) monocrystalline: first weigh 37mg Cu (CH3CN)4PF6Dissolve
In 2mL acetonitrile, then weigh the PPh of Phen and 53mg of 20mg3Part is dissolved in the dichloromethane of 3mL together, then the latter
Solution once adds in former solution, and stirring is filtered after being allowed to react completely, is heavily dissolved in the dichloromethane of 3ml after filtrate rotation being steamed
In, solution covers normal hexane and promotes product to crystallize, after standing a couple of days, separate out a large amount of poles light green color web crystal.Select one
The nearly clear crystal of 0.32mm × 0.30mm × 0.12mm size is tested for x-ray crystal structure.The molecule knot of this compound
Composition is shown graphically in the attached figures 1, and its structure cell packed structures is illustrated in accompanying drawing 2.
To coordination compound Cu (Phen) (PPh3)2(PF6) pure phase crystal prototype carried out a series of performance test.To this
Bright material crystals has carried out steady-state fluorescence test, and result shows that this material, under different excitation wavelength effects, can be launched
Strong green glow, chromaticity coordinates value be chromaticity coordinates value be (0.2505,0.5177), concrete excitation spectrum and emission spectrum such as accompanying drawing
5 and accompanying drawing 6 shown in.And the transient state fluorometric investigation of this material is shown, its luminescent lifetime is 4 microseconds, belongs to phosphorescent emissions.Can
Seeing, this material can be applicable to the green phosphorescent material that multi-wavelength excites, and is also very suitable for the green phosphorus for OLED luminescent layer
Luminescent material.
Claims (5)
1. the cuprous complex luminescent material of green phosphorescent tetrahedral, it is characterised in that: the structural formula of luminescent material is Cu
(Phen)(PPh3)2(PF6), in formula, Phen is that electric neutrality contains N ligand 1,10-Phen, its molecular structure such as formula (I)；In formula
PPh3For electric neutrality ligand triphenylphosphine Han P, its molecular structure such as formula (II):
This luminescent material is monoclinic system, P21/ n (No.14) space group, cell parameter α=90 °, β=92.013 (3) °, γ=90 °,Z=4, Dc=1.429g/cm3, crystal face
Color is light green color；Coordination compound shows as ionic complex, and counter anion therein is hexafluoro-phosphate radical, and cation is then
By cuprous ion and part Phen, PPh3The coordination cation that complexation is formed；In this coordination cation, Cu (I) uses CuN2P2Four
Face body coordination mode, two of which N both is from the Phen part of a bidentate chelating, and two P come from two PPh3Join
Body；Its molecular structure such as formula (III):
The preparation method of the cuprous complex luminescent material of green phosphorescent tetrahedral, the method bag the most according to claim 1
Include following steps:
(1) by Cu (CH under room temperature3CN)4PF6It is completely dissolved in acetonitrile and dichloromethane mixed solvent；
(2) by part Phen and PPh under room temperature3Powder be dissolved completely in dichloromethane；
(3) the two solution is mixed, and stirring is allowed to fully occur complexation reaction；
(4) by reacting liquid filtering, and gained filtrate is quickly revolved under vacuumized conditions after adding normal hexane steaming, remove solvent i.e.
Obtain subdiaphanous fine crystals product.
The most according to claim 2, the preparation method of the cuprous complex luminescent material of green phosphorescent tetrahedral, its feature exists
In: the mol ratio Cu (CH of described three kinds of reactants3CN)4PF6∶Phen∶PPh3It is 1: 1: 2.
The application of the cuprous complex luminescent material of green phosphorescent tetrahedral the most according to claim 1, it is characterised in that institute
State luminescent material and be applied to green glow embedded photoluminescent material.
The application of the cuprous complex luminescent material of green phosphorescent tetrahedral 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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Cited By (2)
| 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 |
Citations (1)
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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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