CN105837626A - Benzoxazolyl isoquinoline cuprous complex orange phosphorescent material - Google Patents
Benzoxazolyl isoquinoline cuprous complex orange phosphorescent material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 61
- BRXWCPVYZSSHPX-UHFFFAOYSA-N 2-isoquinolin-1-yl-1,3-benzoxazole Chemical compound C1=CC=C2C(C=3OC4=CC=CC=C4N=3)=NC=CC2=C1 BRXWCPVYZSSHPX-UHFFFAOYSA-N 0.000 title abstract 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 3
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 14
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 10
- 238000010668 complexation reaction Methods 0.000 claims description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 6
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims description 5
- -1 compound cation Chemical class 0.000 claims description 4
- 238000004020 luminiscence type Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- HUCQPHINKBNKRU-UHFFFAOYSA-N (4-methylphenyl)phosphane Chemical compound CC1=CC=C(P)C=C1 HUCQPHINKBNKRU-UHFFFAOYSA-N 0.000 claims description 2
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims description 2
- 235000000621 Bidens tripartita Nutrition 0.000 claims description 2
- 240000004082 Bidens tripartita Species 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000013522 chelant Substances 0.000 claims description 2
- 208000006637 fused teeth Diseases 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 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
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000011368 organic material Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract 1
- 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
- 239000000243 solution Substances 0.000 abstract 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 30
- 239000011365 complex material Substances 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
- 238000011160 research Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 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
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 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
- 239000013110 organic ligand Substances 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
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002904 solvent Substances 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
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
-
- 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
- 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
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a benzoxazolyl isoquinoline based cuprous complex orange phosphorescent material in a crystal form and a preparation method thereof. The phosphorescent complex is obtained by complexing cuprous salt and a ligand, wherein the molecular structure of the phosphorescent complex is [Cu(2-iQBO)(p-Tol3P)2]PF6; and in the formula, 2-iQBO and p-Tol3P are respectively an electrically neutral heterocyclic ligand benzoxazolyl isoquinoline and tris(p-methylphenyl) phosphine. The complex not only has the advantages of easiness in purification of small molecules and high luminescent efficiency but also has high thermal stability. The material is obtained through direct hybrid reaction between Cu(CH3CN)4PF6 and a dichloromethane solution of the ligand and has the advantages of simple process and equipment, easily obtained raw materials, low cost, and the like. The material can serve as a photoluminescent orange phosphorescent material or a luminescent layer phosphorescent material in an electroluminescent device formed by a plurality of 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
Organic electroluminescent is called for short OEL, is the phenomenon having electric energy to excite organic material and luminescence, as far back as the sixties in last century
Just have been observed that, but do not cause note widely owing to lacking clear and definite application prospect.Deliver since Deng Qingyun in 1987 etc.
After the research work of Organic Light Emitting Diode (OLED), this situation just there occurs dramatical change.Briefly, OLED is
During a kind of electroluminescent formed by multilamellar organic film structure, it is easy to make and has only to relatively low driving electricity
Pressure.OLED is a kind of high brightness, wide vision, the electroluminescent device of all solidstate, has other display devices unrivaled excellent
Point: the most low in energy consumption, OLED is without back lighting, and its power consumption of driver is little；2. fast response time (number microsecond is to tens of microseconds),
Display live image seems most important；3. simple in construction, low cost, it is not necessary to background light source and optical filter, can produce
Ultra-thin, light weight, the product being easy to carry about with one；4. can realize wide viewing angle, high-resolution can be realized and show, high-contrast；5. use
Glass substrate can realize large-area flat-plate and show, as done substrate with flexible material, can make folding display；6. environment is fitted
Ying Xingqiang, has good temperature characterisitic, can display etc. at low ambient temperatures.
During electroluminescent, after electronics and hole-recombination, create singlet state and triplet exciton, according to certainly simultaneously
Rotation Statistical Principles, the ratio of the exciton number of singlet state and triplet is 1: 3, owing to the radiation transistion of triplet exciton is to prohibit
, the triplet exciton luminous efficiency of major part organic material is the lowest, and the efficiency of organic electroluminescence device cannot exceed
25%.Atom centered by metallic element, its coordination compound formed the most effectively can utilize there is multiple electron transition mode
Triplet energies, improves its efficiency, it is achieved close to the 100% of theoretical value.In order to prepare the OLED of high-luminous-efficiency,
People synthesize and have studied substantial amounts of transient metal complex, such as iridium (Ir), gold (Au), platinum (Pt) etc..Up to the present, base
The highest luminous efficiency is maintained in the OLED of phosphorescence Ir coordination compound.But iridium content in nature is the lowest and expensive,
Seriously hinder its commercialization progress.Currently mainly using two kinds of ways to reduce the cost of OLED luminescent layers, one is introduced into having
The metal-free organic molecule of thermic delayed fluorescence effect, excited triplet state energy level and the excited singlet state energy level of this molecule are non-
Very close to, energy therefore can be made to alter the singlet state jumped to radiation between the efficient anti-gap of radiationless triplet, thus carried
The efficiency of high organic electroluminescent.Another kind of way is introduced into the phosphorescent metal complex of low cost, the most cuprous coordination compound.I
State's copper ore resource just has at 910, and gross reserves 62,340,000 tonnage occupies the world the 7th.Have bright for those transition metals
Aobvious advantage, mainly has a following reason putting face: 1, relative to five, the noble metal in six cycles, the aboundresources of Cu, price
Inexpensively, nontoxic little to ambient pressure；2 is identical with complex of iridium, and the theoretical internal quantum efficiency of cuprous coordination compound OLED can reach
100%；3, the coordination mode of Cu (I) coordination compound is the abundantest, respectively with 2,3,4 coordination atoms can be coordinated, forms straight line
Type, plane trigonometry type, the mononuclear complex of tetrahedral structure and the polynuclear complex of the wireless topology such as one-dimensional, two-dimentional, three-dimensional,
Possesses the Photophysics of uniqueness.Therefore, research based on univalent copper complex luminescence new material, there is very important theory
Meaning and actual application value.With Cu (I) coordination compound as phosphor material long-standing (N.Armaroli, G.Accorsi,
F.Cardinali, A.Listorti, Top.Curr.Chem.2007,280,69-115.), this cheap Cu (I) coordination compound
Luminescent material can be prepared easily by Cu (I) ion and suitable organic ligand.Cu (I) coordination compound has abundant chemistry knot
Structure, its coordination mode is changeable, and ligancy is multiple, at different conditions the cuprous coordination compound of available different coordination mode, character
Also differing widely, the research for luminescent material provides more probability.The most at present at OLED operating temperature range Cu (I)
The luminous intensity of complex phosphorescence material does not still reach application demand.Therefore novel cheap Cu (I) complex phosphorescence material is developed
Material has great actual application value.
Summary of the invention
The purpose of present invention is to provide a kind of cuprous complex luminescent material of orange phosphor and preparation method thereof.Pass through
The solution generation complexation reaction of cuprous ion and part, convenient and prepared luminescent properties at a low price and thermal stability is good
Good cuprous complex luminescent material, its orange phosphor luminous intensity is big, Heat stability is good, and its decay of luminescence characteristic is very
Meet the OLED requirement to material phosphorescence luminescent lifetime, be applied to OLED emitting layer material and be conducive to product cost to drop
Low.
One of technical scheme, is to provide a kind of cuprous complex luminescent material of new orange phosphor, by Cu
(CH3CN)4PF6Occur complexation reaction to obtain successively with part, its molecular structure is [Cu (2-iQBO) (p-Tol3P)2]PF6, formula
Middle p-Tol3P is electric neutrality Phosphine ligands three (p-methylphenyl) phosphine, and 2-iQBO is neutral heterocyclic ligand benzoxazolyl group isoquinolin.
Described part benzoxazolyl group isoquinolin, is the coalition of benzothiazole and isoquinolin, its molecular structure such as formula
(I):
In described part, the O in benzothiazole structure has neither part nor lot in coordination, and its atom N and the atom N in isoquinoline structure
Bidentate State is formed with cuprous ion.
Described luminescent material is anorthic system, P-1 space group, and cell parameter is α=83.832 (4) °, β=70.899 (5) °, γ=83.995 (4) °,Z=2, DC
=1.312g/cm3, the crystal color of material is yellow；This luminescent material structure shows as ionic complex, wherein hexafluoro phosphorus
Acid group is counter anion, and cation is then by cuprous ion and part 2-iQBO, p-Tol3P complexation formed coordination sun from
Son；In this coordination compound cation, cuprous ion uses CuN2P2Tetrahedral coordination mode, two of which N is respectively from one
Isoquinolin group in double-tooth chelate ligand 2-iQBO and benzoxazoles group, two P come from another two monodentate phosphine ligand p-
Tol3P；Its molecular structure such as formula (II):
Described luminescent material is applied to orange phosphor material, and this material is by the purple of the widest wave-length coverage (300-550nm)
Exciting of outer light or visible ray, can send the strongest orange-colored light, and its luminescent spectrum presents double-peak feature, and peak emission wavelength divides
Not Wei 580nm and 630nm, chromaticity coordinates is (0.5917,0.4073), and luminescent lifetime is 4.3 microseconds.
The two of technical scheme, are to provide a kind of cuprous complex luminescent material of orange phosphor [Cu (2-iQBO)
(p-Tol3P)2]PF6Preparation method.This preparation method is by Cu (CH3CN)4PF6With part 2-iQBO and p-Tol3The dichloro of P
There is complexation reaction in dichloromethane mixing, finally separates out and obtain the product of crystal powder and realize.Its specific embodiments is divided into
Five steps:
(1) by Cu (CH under room temperature3CN)4PF6Powder is dissolved in dichloromethane；
(2) by p-Tol under room temperature3P powder is dissolved in dichloromethane；
(3) state two kinds of solution mixing by described, and stirring is allowed to fully react, and obtains settled solution A；
(4) under room temperature, 2-iQBO powder is dissolved in dichloromethane, adds mix and blend in solution A, be allowed to abundant
Complexation reaction is occurred to obtain solution B；
(5) in solution B, add normal hexane, be at room temperature evaporated under reduced pressure, vacuum drying, obtain yellow crystals and produce
Thing.
In preparation method of the present invention, the mol ratio Cu (CH of described three kinds of reactants3CN)4PF6∶p-Tol3P: 2-iQBO is 1
∶2∶1。
The cuprous complex luminescent material of the orange phosphor [Cu (2-iQBO) that first beneficial effects of the present invention is provided
(p-Tol3P)2]PF6, the benzothiazole group wherein introduced and isoquinolin group be conducive to molecular-excited state luminous, and Ni metal arrives
The existence of the charge transtion (MLCT) of part effectively facilitates intersystem crossing, and the existence of the groups such as a large amount of phenyl ring, and p-Tol3P
The existence of upper substituent group methyl, causes Cu (I) part around to exist the most sterically hindered, can Inhibitory molecules excited state non-radiative
Decay, part 2-iQBO and p-Tol3P is the part of many aromatic rings, all has a biggest rigidity characteristic, thus this molecular material
The phosphorescent emissions performance having had.This complex material had both possessed advantage that is cheap and that be prone to purification, and had the most molten
Solution property and heat stability, the application further for luminescent material provides technical support.
Beneficial effects of the present invention, next to that prepare the cuprous complex luminescent material of orange phosphor [Cu (2-iQBO) (p-
Tol3P)2]PF6Method, there is simple process, device therefor is simple, and production cost is low, can obtain in a short period of time
The advantages such as the product with very high yield.
Accompanying drawing explanation
Fig. 1. phosphorescent complexes material [Cu (2-iQBO) (p-Tol3P)2]PF6The mono-crystalline structures figure of molecule.
Fig. 2. phosphorescent complexes material [Cu (2-iQBO) (p-Tol3P)2]PF6Molecule is in unit cell and peripheral space
Accumulation graph.
Fig. 3. phosphorescent complexes material [Cu (2-iQBO) (p-Tol3P)2]PF6Ultraviolet-ray visible absorbing (UV-Vis) spectrum
Figure.
Fig. 4. phosphorescent complexes material [Cu (2-iQBO) (p-Tol3P)2]PF6Crystal prototype excites at 470 nano wave length light
The light emission spectrogram of lower mensuration.
Fig. 5. phosphorescent complexes material [Cu (2-iQBO) (p-Tol3P)2]PF6Crystal prototype is under 580 nanometer supervisory wavelength
Measure excites spectrogram.
Fig. 6. phosphorescent complexes material [Cu (2-iQBO) (p-Tol3P)2]PF6Crystal prototype excites at 630 nano wave length light
The light emission spectrogram of lower mensuration.
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 phosphorescent complexes material [Cu (2-iQBO) (p-Tol3P)2]PF6The preparation of crystal prototype: weigh 0.037g
(0.1mmol) Cu (CH3CN)4PF6, the p-Tol of 0.061g (0.2mmol)3The 2-iQBO of P, 0.024g (0.1mmol)；Respectively
Mix successively after dissolving with the dichloromethane of 5ml, be sufficiently stirred for being allowed to fully occur complexation reaction, obtain orange red clarification molten
Liquid；In above-mentioned solution, add a small amount of normal hexane, and at room temperature rotation is evaporated off all solvents, finally give yellow crystals and produce
Thing, productivity is 92% (calculating with Cu).
Embodiment 2
Synthesis orange phosphor complex material [Cu (2-iQBO) (p-Tol3P)2]PF6Monocrystalline: weigh 0.037g
(0.1mmol) Cu (CH3CN)4PF6, the p-Tol of 0.061g (0.2mmol)3The 2-iQBO of P, 0.024g (0.1mmol)；Respectively
Mix successively after dissolving with the dichloromethane of 3ml, be sufficiently stirred for being allowed to fully occur complexation reaction, obtain orange red clarification molten
Liquid；After filtration, solution upper strata cover normal hexane promote product to crystallize, several days standing after have a large amount of yellow bulk crystals to separate out.
The light yellow bulk crystals selecting a 0.40mm*0.36mm*0.30mm size is tested for x-ray crystal structure.This chemical combination
The molecular structure of thing is shown graphically in the attached figures 1, and its structure cell packed structures is illustrated in accompanying drawing 2.
To orange phosphor complex material [Cu (2-iQBO) (p-Tol3P)2]PF6Pure phase crystal prototype carried out some
Row performance test.Material crystals of the present invention has been carried out steady-state fluorescence test, and result shows that this material is at different and excitation wave
Under long effect, can launch strong fluorescent orange, chromaticity coordinates value be (0.5917,0.4073), concrete excitation spectrum with
Emission spectrum is as shown in accompanying drawing 4, accompanying drawing 5 and accompanying drawing 6.And the transient state fluorometric investigation of this material is shown, its luminescent lifetime is 4.3
Microsecond, belongs to phosphorescent emissions.Visible, this material can be applicable to the orange phosphor material that multi-wavelength excites, and is also very suitable for using
Orange phosphor material in OLED luminescent layer.
Claims (4)
1. based on benzoxazolyl group isoquinolin the cuprous coordination compound orange phosphor material of a crystal formation, it is characterised in that: luminous
The structural formula of material is [Cu (2-iQBO) (p-Tol3P)]PF6, p-Tol in formula3P is electric neutrality Phosphine ligands three (p-methylphenyl)
Phosphine；In formula, 2-iQBO is neutral heterocyclic ligand benzoxazolyl group isoquinolin, and this part is benzothiazole and the knot of isoquinolin group
Zoarium, its molecular structure such as formula (I):
Above-mentioned complex phosphorescence material is anorthic system, P-1 space group, and cell parameter is α=83.832 (4) °, β=70.899 (5) °, γ=83.995 (4) °,Z=2, DC=
1.312g/cm3, the crystal color of material is yellow；This luminescent material structure shows as ionic complex, wherein hexafluorophosphoric acid
Root is counter anion, and cation is then by cuprous ion and part 2-iQBO, p-Tol3P complexation formed coordination sun from
Son；In this coordination compound cation, cuprous ion uses CuN2P2Tetrahedral coordination mode, two of which N is respectively from one
Isoquinolin group in double-tooth chelate ligand 2-iQBO and benzoxazoles group, two P come from another two monodentate phosphine ligand p-
Tol3P；Its molecular structure such as formula (II):
The preparation method of the most cuprous coordination compound orange phosphor material, its method comprises the following steps:
(1) by Cu (CH under room temperature3CN)4PF6Powder is dissolved in dichloromethane；
(2) by p-Tol under room temperature3P powder is dissolved in dichloromethane；
(3) state two kinds of solution mixing by described, and stirring is allowed to fully react, and obtains settled solution A；
(4) under room temperature, 2-iQBO powder is dissolved in dichloromethane, adds mix and blend in solution A, be allowed to fully occur
Complexation reaction obtains solution B；
(5) in solution B, add normal hexane, be at room temperature evaporated under reduced pressure, vacuum drying, obtain yellow crystals product.
The preparation method of the most cuprous coordination compound orange phosphor material, it is characterised in that: described three kinds
Mol ratio Cu (the CH of reactant3CN)4PF6∶p-Tol3P: 2-iQBO is 1: 2: 1.
The application of the most cuprous coordination compound orange phosphor material, it is characterised in that described luminescent material
Luminescent spectrum presents double-peak feature, and peak emission wavelength is respectively 580nm and 630nm, can launch luminescence generated by light material as orange light
Material, or it is used as the luminescent layer luminescent material in multilayer electroluminescent device.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610259866.3A CN105837626A (en) | 2016-04-18 | 2016-04-18 | Benzoxazolyl isoquinoline cuprous complex orange phosphorescent material |
Applications Claiming Priority (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 |
| CN108794534A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex orange phosphor luminescent material of BINAP and PBO mixtures |
| CN108795418A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex phosphorescence material of BINAP and aminopyridine mixture |
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| CN103833777A (en) * | 2014-03-20 | 2014-06-04 | 中国计量学院 | Benzoxazolylquinoline ligand-based cuprous complex luminescent material |
| CN104910896A (en) * | 2015-06-17 | 2015-09-16 | 中国计量学院 | Cuprous complex orange red phosphorescent material based on benzoxazolyl quinoline |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103833777A (en) * | 2014-03-20 | 2014-06-04 | 中国计量学院 | Benzoxazolylquinoline ligand-based cuprous complex luminescent material |
| CN104910896A (en) * | 2015-06-17 | 2015-09-16 | 中国计量学院 | Cuprous complex orange red phosphorescent material based on benzoxazolyl quinoline |
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 |
| CN108794534A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex orange phosphor luminescent material of BINAP and PBO mixtures |
| CN108795418A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex phosphorescence material of BINAP and aminopyridine mixture |
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