CN106749400A - The multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex, synthetic method and its application - Google Patents
The multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex, synthetic method and its application Download PDFInfo
- Publication number
- CN106749400A CN106749400A CN201710078381.9A CN201710078381A CN106749400A CN 106749400 A CN106749400 A CN 106749400A CN 201710078381 A CN201710078381 A CN 201710078381A CN 106749400 A CN106749400 A CN 106749400A
- Authority
- CN
- China
- Prior art keywords
- multiple tooth
- electroluminescent
- copper complex
- experiment
- coordination copper
- 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.)
- Granted
Links
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 700
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 350
- 150000004699 copper complex Chemical class 0.000 title claims abstract description 298
- 238000010189 synthetic method Methods 0.000 title claims abstract description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 229
- 239000000975 dye Substances 0.000 claims abstract description 181
- 239000003446 ligand Substances 0.000 claims abstract description 43
- 238000004440 column chromatography Methods 0.000 claims abstract description 16
- 239000003480 eluent Substances 0.000 claims abstract description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003208 petroleum Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 123
- 239000012046 mixed solvent Substances 0.000 claims description 14
- 238000001308 synthesis method Methods 0.000 claims description 10
- KIALCSMRIHRFPL-UHFFFAOYSA-N n-(2,5-diphenylpyrazol-3-yl)-4-nitrobenzamide Chemical compound C1=CC([N+](=O)[O-])=CC=C1C(=O)NC1=CC(C=2C=CC=CC=2)=NN1C1=CC=CC=C1 KIALCSMRIHRFPL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 28
- 239000002184 metal Substances 0.000 abstract description 28
- 230000003111 delayed effect Effects 0.000 abstract description 20
- 230000005284 excitation Effects 0.000 abstract description 19
- 238000009825 accumulation Methods 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 230000000171 quenching effect Effects 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 374
- 238000002347 injection Methods 0.000 description 39
- 239000007924 injection Substances 0.000 description 39
- 238000012360 testing method Methods 0.000 description 33
- 238000000034 method Methods 0.000 description 27
- 230000005540 biological transmission Effects 0.000 description 26
- 230000008021 deposition Effects 0.000 description 26
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 25
- 229910015711 MoOx Inorganic materials 0.000 description 25
- 239000010949 copper Substances 0.000 description 22
- 238000002411 thermogravimetry Methods 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 17
- 229910052802 copper Inorganic materials 0.000 description 17
- 210000004209 hair Anatomy 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 17
- 238000001296 phosphorescence spectrum Methods 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 16
- 239000011521 glass Substances 0.000 description 15
- 235000013350 formula milk Nutrition 0.000 description 14
- 239000004411 aluminium Substances 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000001704 evaporation Methods 0.000 description 13
- 230000008020 evaporation Effects 0.000 description 13
- 230000005525 hole transport Effects 0.000 description 13
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 13
- 230000027756 respiratory electron transport chain Effects 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 238000007738 vacuum evaporation Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000005336 cracking Methods 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 12
- 230000005611 electricity Effects 0.000 description 11
- 230000000630 rising effect Effects 0.000 description 11
- 238000005401 electroluminescence Methods 0.000 description 9
- 238000002189 fluorescence spectrum Methods 0.000 description 9
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 8
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000005424 photoluminescence Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- -1 Shown in Fig. 2 Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000012795 verification Methods 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
- 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
- C07F9/505—Preparation; Separation; Purification; Stabilisation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex, synthetic method and its application, it is related to the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of a class, synthetic method and its application.The present invention is to solve phosphorescence and the caused quenching effect of thermal excitation delayed fluorescence dyestuff exciton accumulation that presently, there are, causing the technical problem of device performance and stability difference.The multiple tooth Phosphine ligands of the dyestuff are part, are coordinated with CuX and constituted, and synthetic method is as follows：The dichloromethane of the multiple tooth Phosphine ligands of 1mmol, the CuX of 0.5~1mmol, 5~10ml is mixed, after 40 45 DEG C are reacted 10~15 hours, is spin-dried for, be that eluent column chromatography is purified with DCM (dichloromethane) and PE (petroleum ether), obtained final product；Increase part to the Quantum geometrical phase of metal using multiple tooth coordination in the present invention, halogen to the electric charge transfer of part is adjusted by halogen, so as to strengthen the phosphorescent emissions of copper complex.
Description
Technical field
The present invention relates to the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of a class, synthetic method and its application.
Background technology
The research of luminous organic material and device causes extensive concern and the further investigation of people.Organic electroluminescent two
Pole pipe (organic light-emitting diodes, OLED) shows and lighting engineering referred to as third generation plane, in energy-conservation
The aspects such as environmental protection have prominent advantage, by the way of are generally at present that electroluminescent phosphorescence is built using phosphorescent coloring, but
Heavy metal involved by phosphorescent coloring is not only expensive but also pollutes environment, in the urgent need to being substituted using other materials.Closely
Phase, it is referred to as thermal excitation delayed fluorescence (the Thermally activated delayed of third generation organic electroluminescent technology
Fluorescenc, TADF) technology makes great progress, in order to effective using the substance produced during electroluminescent
State (Singlet, S1) and triplet (Triplet, T1) exciton, due to obeying statistical probability, i.e. singlet in the raw exciton distribution of electricity
25% and 75% is substantially accounted for respectively with triplet excitons.So, the electroluminescent based on ito glass substrate
The fluorescent device external quantum efficiency of (Electroluminescence, EL) is not over 5%.However, all of exciton is by being
Between alter and alter jump between jump or anti-system and can gather the T of radiation1Or S1Excitation state, so as to realize utilizing 100% exciton.Swash
Sub- utilization rate is to realize the basis of high-performance OLED, for fluorescence (Fluorescenc, FL), phosphorescence (Phosphorescence,
PH) and for thermal excitation delayed fluorescence these three electroluminescent processes, simply by one kind.Or both singlets, or three
The radiation transistion process of line state lights, and the radiation of such single-mode inevitably will respectively produce S for TADF and PH1With
T1The accumulation of exciton.Therefore aggravation singlet-triplet state is buried in oblivion and triplet state-triplet state annihilation (Singlet-triplet and
Triplet-triplet annihilation, STA and TTA) exciton quenching and device efficiency reduction caused by effect.Due to
STA and TTA are directly proportional to exciton concentration.Therefore quenching effect can be suppressed by reducing transient state exciton concentration, based on this
Consider, radiated by binary channels, i.e., the S during electroluminescent1And T1The radiation-curable transition of state, this mode can be realized more
For efficient and rational exciton is distributed, device performance is improved.In view of T1State exciton is in the great majority when primary state is played, double electroluminescent hairs of transmitting
Photoinitiator dye must circulate the S being only possible to realize truly by altering to alter to jump between jump and anti-gap between the gap of reasonable control1State swashs
Son and T1The optimal allocation of state exciton, and then balance and the coordination of TADF, PH transmitting are realized, therefore, how to build real meaning
On biradial electroluminescent material be still a very big challenge.
It is well known that most of copper complex is heating excites delayed fluorescence or phosphorescent, few copper are matched somebody with somebody
The characteristics of compound had not only had the property of thermal excitation delayed fluorescence but also had double transmittings of phosphorescence, chief reason is exactly copper complex
In copper ion and part between Quantum geometrical phase it is weaker, so hardly result in effective phosphorescent emissions, but, current copper
Complex does not develop the electroluminescent dyestuff of double transmittings yet, there is provided an extraordinary platform.This work is not only embodied
The compellent superiority in terms of exciton utilization rate of double emissive materials, while also demonstrating the feasible way of transmitting ratio modulation
Footpath is feasible, and this lays a good foundation for the further development and application of such luminescent material.
The content of the invention
The present invention is to solve the phosphorescence that presently, there are and sudden caused by the accumulation of thermal excitation delayed fluorescence dyestuff exciton
Go out effect, cause the technical problem of device performance and stability difference, there is provided a kind of multiple tooth double transmitting electricity of phosphine coordination copper complex
Photoluminescence Dyestuff synthesis method and its application.
The double transmitting electroluminescent dyestuffs of multiple tooth phosphine coordination copper complex, it is characterised in that the dyestuff with multiple tooth Phosphine ligands with
CuX coordinations are constituted, and molecular structural formula is as follows：
The multiple tooth Phosphine ligands are DPA, PPADP, PPPADP or DPAP, and wherein X is Cl, Br or I.
The synthetic method is as follows：
The dichloromethane of the multiple tooth Phosphine ligands of 1mmol, the CuX of 0.5~1mmol, 5~10ml is mixed, 40-45 DEG C of reaction 10
After~15 hours, it is spin-dried for, with dichloromethane (DCM) and petroleum ether (PE) for eluent column chromatography is purified, obtains multiple tooth phosphine coordination
Copper complex；
The multiple tooth Phosphine ligands are DPA, PPADP, PPPADP or DPAP, and wherein X is Cl, Br or I.
Described multiple tooth Phosphine ligands are (1~2) ﹕ 1 with the amount ratio of the material of CuX.Described DCM (dichloromethane) and PE
The volume ratio of DCM and PE is 1 ﹕ 20 in the mixed solvent of (petroleum ether).
The multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex are used to prepare as the guest materials of luminescent layer
Electroluminescent device.The characteristics of multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of the invention have double transmittings, both
Thermal excitation delayed fluorescence can be launched can also launch phosphorescence, because its singlet and triplet state can transition, Ke Yitong simultaneously
Shi Liyong singlets and triplet excitons, and the dynamically distributes of exciton are realized during electroluminescent, so as to realize maximum limit
The accumulation of the reduction exciton of degree, improves device efficiency, and the efficiency roll-off of suppression device realizes the maximum profit during electroluminescent
With.Increase part to the Quantum geometrical phase of metal using multiple tooth coordination in the present invention, halogen is adjusted by halogen to matching somebody with somebody
The electric charge transfer of body, so as to strengthen the phosphorescent emissions of copper complex, finally gives a thermal excitation delayed fluorescence and phosphorescence all has
The performance of standby double transmittings.Increase the conjugated degree of part by increasing phenyl ring simultaneously to adjust the luminous face of copper complex
Color.The multiple tooth phosphine double transmitting electroluminescent dyestuff electroluminescent materials of coordination copper complex prepared by the present invention can realize ultralow pressure
The high efficiency electroluminous device of driving, external quantum efficiency reaches maximum 20.5%.
The multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of the present invention are used for the electroluminescent of electroluminescent device
Guest materials includes advantages below：
1st, can be as object, for the luminescent layer of electroluminescent device.
2nd, the performance of electroluminescent device material is improved, with the double transmitting electroluminescent dyestuff visitors of multiple tooth phosphine coordination copper complex
Electroluminescent device prepared by body material has good thermodynamic stability, and cracking temperature is 338 DEG C -446 DEG C, while having
The characteristics of double transmittings.Luminous efficiency and the brightness of electroluminescent organic material are improve, present invention is mainly applied to organic electroluminescence
In LED device.
Brief description of the drawings
Fig. 1 is the ultraviolet of the multiple tooth phosphine double transmitting electroluminescent dyestuffs of coordination copper complex in experiment one, experiment two, experiment three
Fluorescence spectrum spectrogram, the fluorescence spectra being dissolved in dichloromethane solvent and phosphorescence spectrum figure, ■ ● ▲ respectively represent experiment one,
Ultraviolet spectra of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in dichloromethane solvent in experiment two, experiment three
Figure, the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex are molten during the △ of zero represent experiment one, experiment two, experiment three respectively
Fluorescence spectra in dichloromethane solvent；Fig. 2 is that multiple tooth phosphine coordination copper coordinates in representing experiment one, experiment two, experiment three
The thermogravimetric analysis figures of the double transmitting electroluminescent dyestuffs of thing, ■ ◆ ▲ represent experiment one, experiment two, experiment three respectively in multiple tooth phosphine match somebody with somebody
The thermogravimetric analysis figure of the double transmitting electroluminescent dyestuffs of position copper complex；Fig. 3 be experiment four, experiment five, experiment six in multiple tooth phosphine match somebody with somebody
The Ultraluminescence spectrum spectrogram of the double transmitting electroluminescent dyestuffs of position copper complex, is dissolved in the fluorescence spectra in dichloromethane solvent
With phosphorescence spectrum figure, ■ ● ▲ represent experiment four, experiment five, experiment six respectively in the double transmittings of coordination copper complex of multiple tooth phosphine it is electroluminescent
Ultraviolet spectrogram of the luminescent dye in dichloromethane solvent, the △ of zero represent respectively experiment four, experiment five, experiment six in it is multiple tooth
The double transmitting electroluminescent dyestuffs of phosphine coordination copper complex are dissolved in the fluorescence spectra in dichloromethane solvent, and ☆ ★ ◇ are represented respectively
The multiple tooth double transmitting electroluminescent phosphorescence of dyes spectrograms of phosphine coordination copper complex in experiment four, experiment five, experiment six；Fig. 4 is
Represent the thermogravimetric analysis figure of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in experiment four, experiment five, experiment six, ■
◆ ▲ respectively represents the thermogravimetric of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in experiment four, experiment five, experiment six
Analysis chart；Fig. 5 is the ultraviolet of the multiple tooth phosphine double transmitting electroluminescent dyestuffs of coordination copper complex in experiment seven, experiment eight, experiment nine
Fluorescence spectrum spectrogram, the fluorescence spectra being dissolved in dichloromethane solvent and phosphorescence spectrum figure, ■ ● ▲ respectively represent experiment seven,
Ultraviolet spectra of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in dichloromethane solvent in experiment eight, experiment nine
Figure, the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex are molten during the △ of zero represent experiment seven, experiment eight, experiment nine respectively
Fluorescence spectra in dichloromethane solvent, ☆ ★ ◇ represent multiple tooth phosphine coordination copper in experiment seven, experiment eight, experiment nine respectively
The double transmitting electroluminescent phosphorescence of dyes spectrograms of complex；Fig. 6 is that multiple tooth phosphine is matched somebody with somebody in representing experiment seven, experiment eight, experiment nine
The thermogravimetric analysis figures of position copper complex pair transmitting electroluminescent dyestuffs, ■ ◆ ▲ represent experiment seven, experiment eight respectively, test in nine
The thermogravimetric analysis figure of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex；Fig. 7 is experiment ten, experiment 11, experiment ten
The Ultraluminescence spectrum spectrogram of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex, is dissolved in dichloromethane solvent in two
Fluorescence spectra and phosphorescence spectrum figure, ■ ● ▲ represent multiple tooth phosphine coordination copper in experiment ten, experiment 11, experiment 12 respectively
Ultraviolet spectrograms of the double transmitting electroluminescent dyestuffs of complex in dichloromethane solvent, the △ of zero represent experiment ten, reality respectively
Test the fluorescence that the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex are dissolved in dichloromethane solvent in 11, experiment 12
Spectrogram, ☆ ★ ◇ represent the multiple tooth double electroluminescent hairs of transmitting of phosphine coordination copper complex in experiment ten, experiment 11, experiment 12 respectively
The phosphorescence spectrum figure of photoinitiator dye；Fig. 8 is to represent the multiple tooth double hairs of phosphine coordination copper complex in experiment ten, experiment 11, experiment 12
The thermogravimetric analysis figure of radio photoluminescence dyestuff, ■ ◆ ▲ multiple tooth phosphine coordination in experiment ten, experiment 11, experiment 12 is represented respectively
The thermogravimetric analysis figure of the double transmitting electroluminescent dyestuffs of copper complex；Fig. 9 is multiple tooth phosphine coordination in experiment one, experiment two, experiment three
The voltage-current density relation curve of the electroluminescent device of the double transmitting electroluminescent dyestuffs of copper complex, ■ ● ▲ difference table
Show the electroluminescent device of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in experiment one, experiment two, experiment three
Voltage-current density relation curve；Figure 10 is the multiple tooth double transmitting electricity of phosphine coordination copper complex in experiment one, experiment two, experiment three
The voltage-brightness relation curve of the electroluminescent device of photoluminescence dyestuff, ■ ● ▲ experiment one, experiment two, experiment are represented respectively
The voltage-brightness relation curve of the electroluminescent device of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in three；Figure
11 is the electroluminescent device of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in experiment one, experiment two, experiment three
Luminance-current efficiency relation curve, ■ ● ▲ represent experiment one, experiment two, experiment three respectively in multiple tooth phosphine coordination copper coordinate
The luminance-current efficiency relation curve of the electroluminescent device of the double transmitting electroluminescent dyestuffs of thing；Figure 12 is experiment one, experiment
2nd, multiple tooth phosphine coordination copper complex pair launches the brightness-power efficiency of the electroluminescent devices of electroluminescent dyestuffs in experiment three
Relation curve, ■ ● ▲ the multiple tooth double transmitting electroluminescent of phosphine coordination copper complex in experiment one, experiment two, experiment three are represented respectively
Brightness-the power efficiency relation curve of the electroluminescent device of dyestuff；Figure 13 is multiple tooth phosphine in experiment one, experiment two, experiment three
The current density of the electroluminescent device of the double transmitting electroluminescent dyestuffs of coordination copper complex-external quantum efficiency relation curve effect
Rate, ■ ● ▲ represent experiment one, experiment two respectively, test the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in three
The current density of electroluminescent device-external quantum efficiency relation curve efficiency；Figure 14 be experiment one, experiment two, experiment three in it is many
The electroluminescent light spectrogram of the electroluminescent device of the double transmitting electroluminescent dyestuffs of tooth phosphine coordination copper complex, ■ ● ▲ difference table
Show the electroluminescent device of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in experiment one, experiment two, experiment three
Electroluminescent light spectrogram；Figure 15 is the multiple tooth double transmitting electroluminescent dyes of phosphine coordination copper complex in experiment four, experiment five, experiment six
The voltage-current density relation curve of the electroluminescent device of material, ■ ● ▲ represent experiment four, experiment five respectively, test in six
The voltage-current density relation curve of the electroluminescent device of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex；Figure
16 is the electroluminescent device of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in experiment four, experiment five, experiment six
Voltage-brightness relation curve, ■ ● ▲ represent experiment four, experiment five, experiment six respectively in multiple tooth phosphine coordination copper complex it is double
Launch the voltage-brightness relation curve of the electroluminescent device of electroluminescent dyestuff；Figure 17 is experiment four, experiment five, experiment six
In the multiple tooth phosphine double transmitting electroluminescent dyestuffs of coordination copper complex electroluminescent devices luminance-current efficiency relation curve,
■ ● ▲ represent experiment four, experiment five respectively, test the electricity of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in six
The luminance-current efficiency relation curve of electroluminescence device；Figure 18 is that multiple tooth phosphine coordination copper is matched somebody with somebody in experiment four, experiment five, experiment six
Brightness-the power efficiency relation curve of the electroluminescent device of the double transmitting electroluminescent dyestuffs of compound, ■ ● ▲ represent real respectively
Test four, experiment five, in experiment six electroluminescent devices of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex brightness-
Power efficiency relation curve；Figure 19 is that the double transmittings of coordination copper complex of multiple tooth phosphine are electroluminescent in experiments experiment four, experiment five, experiment six
The current density of the electroluminescent device of luminescent dye-external quantum efficiency relation curve efficiency, ■ ● ▲ represent that experiment is real respectively
Test the electric current of the electroluminescent device of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in four, experiment five, experiment six
Density-external quantum efficiency relation curve efficiency；Figure 20 is multiple tooth phosphine coordination copper complex pair in experiment four, experiment five, experiment six
Launch the electroluminescent light spectrogram of the electroluminescent device of electroluminescent dyestuff, ■ ● ▲ experiment four, experiment five, real is represented respectively
Test the electroluminescent light spectrogram of the electroluminescent device of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in six；Figure 21
It is the electroluminescent device of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in experiment seven, experiment eight, experiment nine
Voltage-current density relation curve, ■ ● ▲ multiple tooth phosphine coordination copper complex in experiment seven, experiment eight, experiment nine is represented respectively
The voltage-current density relation curve of the electroluminescent device of double transmitting electroluminescent dyestuffs；Figure 22 be experiment seven, experiment eight,
The voltage-brightness relation of the electroluminescent device of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex is bent in experiment nine
Line, ■ ● ▲ represent experiment seven, experiment eight respectively, test the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in nine
The voltage-brightness relation curve of electroluminescent device；Figure 23 is multiple tooth phosphine coordination copper cooperation in experiment seven, experiment eight, experiment nine
The luminance-current efficiency relation curve of the electroluminescent device of the double transmitting electroluminescent dyestuffs of thing, ■ ● ▲ experiment is represented respectively
7th, multiple tooth phosphine coordination copper complex pair launches the brightness-electricity of the electroluminescent devices of electroluminescent dyestuffs in experiment eight, experiment nine
Stream relationship between efficiency curve；Figure 24 is the multiple tooth double transmitting electroluminescent dyes of phosphine coordination copper complex in experiment seven, experiment eight, experiment nine
Brightness-the power efficiency relation curve of the electroluminescent device of material, ■ ● ▲ represent experiment seven, experiment eight respectively, test in nine
Brightness-the power efficiency relation curve of the electroluminescent device of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex；Figure
25 is the electroluminescent device of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in experiment seven, experiment eight, experiment nine
Current density-external quantum efficiency relation curve efficiency, ■ ● ▲ represent multiple tooth phosphine in experiment seven, experiment eight, experiment nine respectively
The current density of the electroluminescent device of the double transmitting electroluminescent dyestuffs of coordination copper complex-external quantum efficiency relation curve effect
Rate；Figure 26 is the electroluminescent of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in experiment seven, experiment eight, experiment nine
The electroluminescent light spectrogram of device, ■ ● ▲ represent experiment seven, experiment eight, experiment nine respectively in multiple tooth phosphine coordination copper complex it is double
Launch the electroluminescent light spectrogram of the electroluminescent device of electroluminescent dyestuff；Figure 27 is experiment ten, experiment 11, experiment 12
In the multiple tooth phosphine double transmitting electroluminescent dyestuffs of coordination copper complex electroluminescent devices voltage-current density relation curve,
■ ● ▲ the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in experiment ten, experiment 11, experiment 12 are represented respectively
Electroluminescent device voltage-current density relation curve；Figure 28 is multiple tooth phosphine in experiment ten, experiment 11, experiment 12
The voltage-brightness relation curve of the electroluminescent device of the double transmitting electroluminescent dyestuffs of coordination copper complex, ■ ● ▲ difference table
Show the electroluminescent cell of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in experiment ten, experiment 11, experiment 12
The voltage-brightness relation curve of part；Figure 29 is the multiple tooth double hairs of phosphine coordination copper complex in experiment ten, experiment 11, experiment 12
The luminance-current efficiency relation curve of the electroluminescent device of radio photoluminescence dyestuff, ■ ● ▲ experiment ten, experiment are represented respectively
11, multiple tooth phosphine coordination copper complex pair launches the luminance-current of the electroluminescent devices of electroluminescent dyestuffs in experiment 12
Relationship between efficiency curve；Figure 30 is the multiple tooth double transmitting electroluminescent of phosphine coordination copper complex in experiment ten, experiment 11, experiment 12
Brightness-the power efficiency relation curve of the electroluminescent device of dyestuff, ■ ● ▲ experiment ten, experiment 11, experiment are represented respectively
Brightness-power efficiency the relation of the electroluminescent device of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex is bent in 12
Line；Figure 31 is the electroluminescent of the multiple tooth phosphine double transmitting electroluminescent dyestuffs of coordination copper complex in experiment ten, experiment 11, experiment 12
The current density of luminescent device-external quantum efficiency relation curve efficiency, ■ ● ▲ experiment ten, experiment 11, experiment are represented respectively
Current density-the external quantum efficiency of the electroluminescent device of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in 12
Relation curve efficiency；Figure 32 is the multiple tooth double transmitting electroluminescent of phosphine coordination copper complex in experiment ten, experiment 11, experiment 12
The electroluminescent light spectrogram of the electroluminescent device of dyestuff, ■ ● ▲ respectively represent experiment ten, experiment 11, experiment 12 in it is many
The electroluminescent light spectrogram of the electroluminescent device of the double transmitting electroluminescent dyestuffs of tooth phosphine coordination copper complex；Figure 33 is experiment one
In the multiple tooth phosphine double transmitting electroluminescent dyestuffs of coordination copper complex alternating temperature life-span spectrograms；Figure 34 is multiple tooth phosphine coordination in experiment two
The alternating temperature life-span spectrogram of the double transmitting electroluminescent dyestuffs of copper complex；Figure 35 is the multiple tooth double hairs of phosphine coordination copper complex in experiment three
The alternating temperature life-span spectrogram of radio photoluminescence dyestuff；Figure 36 is the multiple tooth double transmitting electroluminescent dyes of phosphine coordination copper complex in experiment four
The alternating temperature life-span spectrogram of material；Figure 37 is the alternating temperature life-span for testing the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in five
Spectrogram；Figure 38 is the alternating temperature life-span spectrogram for testing the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in six；Figure 39 is
The alternating temperature life-span spectrogram of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in experiment seven；Figure 40 is multiple tooth in testing eight
The alternating temperature life-span spectrogram of the double transmitting electroluminescent dyestuffs of phosphine coordination copper complex；Figure 41 is multiple tooth phosphine coordination copper cooperation in experiment nine
The alternating temperature life-span spectrogram of the double transmitting electroluminescent dyestuffs of thing；Figure 42 is that the multiple tooth double transmittings of phosphine coordination copper complex are electroluminescent in testing ten
The alternating temperature life-span spectrogram of luminescent dye；Figure 43 is the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in experiment 11
Alternating temperature life-span spectrogram；Figure 44 is the alternating temperature life spectrum for testing the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex in 12
Figure.
Specific embodiment
Technical solution of the present invention is not limited to act specific embodiment set forth below, also including between each specific embodiment
Any combination.
Specific embodiment one：The multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of present embodiment, the dyestuff
Constituted with multiple tooth Phosphine ligands and CuX coordinations, molecular structural formula is as follows：
The multiple tooth Phosphine ligands be DPA,
PPADP, PPPADP or DPAP, wherein X are Cl, Br or I.
Specific embodiment two：The double transmitting electroluminescent dyes of multiple tooth phosphine coordination copper complex described in specific embodiment one
Material synthetic method：
The dichloromethane of the multiple tooth Phosphine ligands of 1mmol, the CuX of 0.5~1mmol, 5~10ml is mixed, 40-45 DEG C of reaction 10
After~15 hours, it is spin-dried for, is purified by eluent column chromatography of DCM and PE, obtains multiple tooth phosphine coordination copper complex；
The multiple tooth Phosphine ligands are DPA, PPADP, PPPADP or DPAP, and wherein X is Cl, Br or I.
Specific embodiment three：Present embodiment and multiple tooth Phosphine ligands described unlike specific embodiment two with
The amount ratio of the material of CuX is (1~2) ﹕ 1.Other are identical with specific embodiment two.
Specific embodiment four：Present embodiment and multiple tooth Phosphine ligands described unlike specific embodiment two with
The amount ratio of the material of CuX is 1 ﹕ 1.Other are identical with specific embodiment two.
Specific embodiment five：The mixing of present embodiment and DCM and PE described unlike specific embodiment two
The volume ratio of DCM and PE is 1 ﹕ 20 in solvent.Other are identical with specific embodiment two.
Specific embodiment six：Present embodiment is reacted 12 hours from unlike specific embodiment two at 42 DEG C.Its
He is identical with specific embodiment two.
Specific embodiment seven：Present embodiment is reacted 13 hours from unlike specific embodiment two at 43 DEG C.Its
He is identical with specific embodiment two.
Specific embodiment eight：Present embodiment is reacted 14 hours from unlike specific embodiment two at 44 DEG C.Its
He is identical with specific embodiment two.
Specific embodiment nine：Present embodiment is reacted 15 hours from unlike specific embodiment two at 45 DEG C.Its
He is identical with specific embodiment two.
Specific embodiment ten：The multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex described in specific embodiment one
It is used to prepare electroluminescent device as the guest materials of luminescent layer.
The multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex are used to make as luminescent layer described in present embodiment
The method of standby electro phosphorescent device is as follows：
First, the glass or plastic supporting base that are cleaned through deionized water are put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar,
Evaporation rate is set to 0.1~0.3nm.s-1, on glass or plastic supporting base deposition material be tin indium oxide (ITO), thickness be 1~
The anode conductive layer of 100nm；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 2~10nm hole injection layers；
3rd, hole transport layer material TAPC is deposited with hole injection layer, thickness is obtained for 20~40nm hole transmission layers；
4th, multiple tooth double transmitting electroluminescent dyestuff and the material of main parts of phosphine coordination copper complex are deposited with hole transmission layer
MCP mixes, and obtains thickness for 5~15nm；
5th, electron transport layer materials TPBi is deposited with luminescent layer, thickness is 10~80nm electron transfer layers；
6th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 1~10nm electron injecting layers；
7th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 1~100nm, obtains electroluminescent hair
Optical device.
Metal described in step 7 is calcium, magnesium, copper, aluminium, calcium alloy, magnesium alloy, copper alloy or aluminium alloy.
Using following experimental verifications effect of the present invention：
Experiment one：The synthetic method of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of this experiment follow these steps to
Realize：
The DCM of the multiple tooth Phosphine ligands of 1mmol, CuCl, 5ml of 1mmol is mixed, after 40 DEG C are reacted 10~15 hours, is spin-dried for,
Purified by eluent column chromatography of DCM and PE, obtain multiple tooth phosphine coordination copper complex；
Wherein described multiple tooth Phosphine ligands are 1 ﹕ 1 with the amount ratio of CuCl.
The volume ratio of DCM and PE is 1 ﹕ 20 in described DCM and the mixed solvent of PE.
The multiple tooth phosphine coordination copper complex pair that this experiment is obtained launches electroluminescent Dyes structural formulaes and is
It is DPACuCl that this experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex.
The DPACuCl modified using the multifunction of Mass Spectrometer Method this experiment preparation, testing result is as follows：
m/z:1288.13 (100.0%), 1290.13 (89.1%), 1289.13 (82.2%), 1291.13 (73.3%),
1290.13 (63.9%), 1292.13 (57.0%), 1291.13 (52.5%), 1293.13 (46.8%), 1290.14
(33.3%), 1292.14 (29.7%), 1292.13 (21.3%), 1292.13 (19.9%), 1294.13 (19.0%),
1293.13 (16.3%), 1294.12 (12.7%), 1295.13 (10.4%), 1292.12 (10.2%), 1294.12
(9.1%), 1291.14 (8.9%), 1293.13 (8.4%), 1293.14 (7.9%), 1295.13 (7.5%), 1294.13
(6.6%), 1293.14 (5.2%), 1295.14 (4.6%), 1296.13 (4.2%), 1294.13 (3.4%), 1296.13
(3.0%), 1296.12 (2.0%), 1295.14 (1.8%), 1297.12 (1.7%), 1292.14 (1.4%), 1294.14
(1.3%), 1294.14 (1.1%), 1297.13 (1.0%), 1296.14 (1.0%).Elemental Analysis (%)
for:C76H56Cu2Cl2P4:C,70.70；H,4.37.
This experiment obtains the Ultraluminescence spectrum of the multiple tooth double transmitting electroluminescent dyestuff DPACuCl of phosphine coordination copper complex,
Phosphorescence spectrum spectrogram is as shown in Figure 1.This experiment obtains the multiple tooth double transmitting electroluminescent dyestuff DPACuCl's of phosphine coordination copper complex
Thermogravimetric analysis spectrogram launches splitting for electroluminescent dyestuff DPACuCl as shown in Fig. 2 multiple tooth phosphine coordination copper complex is double as seen from the figure
Solution temperature is 407 DEG C.
The multiple tooth double transmitting electroluminescent dyestuff DPACuCl of phosphine coordination copper complex are used to prepare electroluminescent as luminescent layer
The method of device is as follows：
First, the plastic supporting base cleaned through deionized water is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed
Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is the anode conducting of 10nm
Layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material TAPC is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, multiple tooth double transmitting electroluminescent dyestuff and the material of main parts of phosphine coordination copper complex are deposited with hole transmission layer
MCP mixes, and obtains thickness for 15nm；
5th, electron transport layer materials TPBi is deposited with luminescent layer, thickness is 80nm electron transfer layers；
6th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
7th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device
Part.Metal described in step 7 is aluminium.The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/TAPC
(40nm)/mCP:DPACuCl(15nm)/TPBi(80nm)/LiF(10nm)/Al.This experiment is double with multiple tooth phosphine coordination copper complex
The voltage-current density relation curve of electroluminescent device prepared by transmitting electroluminescent dyestuff DPACuCl as shown in figure 9, by
This figure understands that the multiple tooth double transmitting electroluminescent dyestuff DPACuCl materials of phosphine coordination copper complex have characteristic of semiconductor, its threshold values
Voltage is 4V.The electroluminescent cell that this experiment is prepared with the double transmitting electroluminescent dyestuff DPACuCl of multiple tooth phosphine coordination copper complex
As shown in Figure 10, thus figure understands that the bright voltage that opens of the device is 4V to the voltage-brightness relation curve of part.This experiment is with multiple tooth phosphine
The luminance-current efficiency relation of electroluminescent device prepared by the double transmitting electroluminescent dyestuff DPACuCl of coordination copper complex is bent
As shown in figure 11, thus figure understands that the device is 2.4cdm in brightness to line-2When, current efficiency reaches maximum 11.8cdA-1.This experiment is bright with the electroluminescent device of the double transmitting electroluminescent dyestuff DPACuCl preparations of multiple tooth phosphine coordination copper complex
As shown in figure 12, thus figure understands that the device is 2.1cdm in brightness to degree-power efficiency relation curve-2When, power efficiency reaches
To maximum 6lmW-1.This experiment is electroluminescent with the double transmitting electroluminescent dyestuff DPACuCl preparations of multiple tooth phosphine coordination copper complex
As shown in figure 13, thus figure understands that the device is 6mA in brightness to the current density of luminescent device-external quantum efficiency relation curve
cm-2When, obtain maximum external quantum efficiency 14.3%.This experiment is with the multiple tooth phosphine double transmitting electroluminescent dyestuffs of coordination copper complex
As shown in figure 14, thus figure understands the electroluminescent hair of the device to the electroluminescent light spectrogram of electroluminescent device prepared by DPACuCl
Photopeak is at 605nm.Knowable to this Figure 33：As temperature is raised, the life-span drastically declines, and is at low temperature phosphorescent emissions, with
The rising of temperature, shows thermal excitation delayed fluorescence property, so as to embody double transmittings.
Experiment two：The synthetic method of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of this experiment follow these steps to
Realize：
The DCM of the multiple tooth Phosphine ligands of 1mmol, CuBr, 5ml of 1mmol is mixed, after 40~45 DEG C are reacted 10~15 hours,
It is spin-dried for, is purified by eluent column chromatography of DCM and PE, obtains multiple tooth phosphine coordination copper complex；
Wherein described multiple tooth Phosphine ligands are 1 ﹕ 1 with the amount ratio of CuBr.
The volume ratio of DCM and PE is 1 ﹕ 20 in described DCM and the mixed solvent of PE.
The multiple tooth phosphine coordination copper complex pair that this experiment is obtained launches electroluminescent Dyes structural formulaes and is
It is DPACuBr that this experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex.
The DPACuBr modified using the multifunction of Mass Spectrometer Method this experiment preparation, testing result is as follows：
m/z:1378.03 (100.0%), 1380.03 (89.1%), 1379.03 (79.0%), 1381.03 (70.4%),
1376.03 (51.4%), 1380.03 (48.6%), 1378.03 (45.8%), 1382.02 (43.4%), 1377.03
(42.2%), 1381.03 (40.0%), 1383.03 (35.6%), 1380.03 (26.4%), 1382.03 (23.6%),
1379.03 (20.8%), 1382.02 (19.9%), 1379.03 (16.8%), 1378.04 (16.4%), 1383.03
(15.7%), 1380.03 (14.6%), 1382.03 (14.5%), 1384.03 (14.5%), 1380.03 (10.2%),
1384.02 (9.7%), 1381.04 (8.7%), 1385.02 (7.9%), 1383.04 (7.7%), 1380.03 (6.9%),
1382.03 (6.1%), 1384.03 (5.3%), 1381.03 (4.6%), 1379.04 (4.6%), 1381.04 (4.1%),
1381.03 (3.8%), 1383.04 (3.5%), 1382.03 (3.4%), 1379.03 (3.2%), 1385.03 (3.1%),
1381.03 (2.9%), 1386.03 (2.9%), 1382.04 (1.7%), 1385.03 (1.7%), 1382.03 (1.7%),
1384.04 (1.6%), 1384.03 (1.4%).Elemental Analysis (%) for:C76H56Cu2Br2P4:C,66.14；
H,4.09。
This experiment obtains the Ultraluminescence spectrum of the multiple tooth double transmitting electroluminescent dyestuff DPACuBr of phosphine coordination copper complex,
Phosphorescence spectrum spectrogram is as shown in Figure 1.
This experiment obtains the thermogravimetric analysis spectrogram of the multiple tooth double transmitting electroluminescent dyestuff DPACuBr of phosphine coordination copper complex such as
Shown in Fig. 2, the cracking temperature of the multiple tooth double transmitting electroluminescent dyestuff DPACuBr of phosphine coordination copper complex is 403 DEG C as seen from the figure.
The multiple tooth double transmitting electroluminescent dyestuff DPACuBr of phosphine coordination copper complex are used to prepare electroluminescent as luminescent layer
The method of device is as follows：
First, the plastic supporting base cleaned through deionized water is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed
Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is the anode conducting of 10nm
Layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material TAPC is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, multiple tooth double transmitting electroluminescent dyestuff and the material of main parts of phosphine coordination copper complex are deposited with hole transmission layer
MCP mixes, and obtains thickness for 15nm；
5th, electron transport layer materials TPBi is deposited with luminescent layer, thickness is 80nm electron transfer layers；
6th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
7th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device
Part.Metal described in step 7 is aluminium.The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/TAPC
(40nm)/mCP:DPACuBr(15nm)/TPBi(80nm)/LiF(10nm)/Al.This experiment is double with multiple tooth phosphine coordination copper complex
The voltage-current density relation curve of electroluminescent device prepared by transmitting electroluminescent dyestuff DPACuBr as shown in figure 9, by
This figure understands that the multiple tooth double transmitting electroluminescent dyestuff DPACuBr materials of phosphine coordination copper complex have characteristic of semiconductor, its threshold values
Voltage is 3.8V.The electroluminescent that this experiment is prepared with the double transmitting electroluminescent dyestuff DPACuBr of multiple tooth phosphine coordination copper complex
As shown in Figure 10, thus figure understands that the bright voltage that opens of the device is 4V to the voltage-brightness relation curve of device.This experiment is with multiple tooth
The luminance-current efficiency relation of electroluminescent device prepared by the double transmitting electroluminescent dyestuff DPACuBr of phosphine coordination copper complex
As shown in figure 11, thus figure understands that the device is 2.6cdm in brightness to curve-2When, current efficiency reaches maximum 13cdA-1.This experiment is bright with the electroluminescent device of the double transmitting electroluminescent dyestuff DPACuBr preparations of multiple tooth phosphine coordination copper complex
As shown in figure 12, thus figure understands that the device is 2.1cdm in brightness to degree-power efficiency relation curve-2When, power efficiency reaches
To maximum 6.8lmW-1.The electricity that this experiment is prepared with the double transmitting electroluminescent dyestuff DPACuBr of multiple tooth phosphine coordination copper complex
As shown in figure 13, thus figure understands that the device is in brightness to the current density of electroluminescence device-external quantum efficiency relation curve
6mA·cm-2When, obtain maximum external quantum efficiency 12.8%.This experiment is with the double transmitting electroluminescent of coordination copper complex of multiple tooth phosphine
As shown in figure 14, thus figure understands the electricity of the device to the electroluminescent light spectrogram of electroluminescent device prepared by dyestuff DPACuBr
Photoluminescence peak is at 608nm.As can be seen from Figure 34：As temperature is raised, the life-span drastically declines, and is at low temperature phosphorescent emissions, with
The rising of temperature, thermal excitation delayed fluorescence property is shown, so as to embody double transmittings.
Experiment three：The synthetic method of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of this experiment follow these steps to
Realize：
The DCM of the multiple tooth Phosphine ligands of 1mmol, CuI, 5ml of 1mmol is mixed, after 40~45 DEG C are reacted 10~15 hours, rotation
It is dry, purified by eluent column chromatography of DCM and PE, obtain multiple tooth phosphine coordination copper complex；
Wherein described multiple tooth Phosphine ligands are 1 ﹕ 1 with the amount ratio of CuI.
The volume ratio of DCM and PE is 1 ﹕ 20 in described DCM and the mixed solvent of PE.
The multiple tooth phosphine coordination copper complex pair that this experiment is obtained launches electroluminescent Dyes structural formulaes and is
It is DPACuI that this experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex.
The DPACuI modified using the multifunction of Mass Spectrometer Method this experiment preparation, testing result is as follows：
m/z:1472.00 (100.0%), 1473.00 (82.2%), 1475.00 (73.3%), 1474.00 (44.6%),
1474.00 (44.6%), 1474.01 (33.3%), 1476.00 (19.9%), 1477.00 (16.3%), 1476.01
(14.9%), 1476.01 (14.9%), 1475.01 (8.9%), 1477.01 (7.6%), 1478.00 (6.6%), 1479.01
(1.8%), 1476.01 (1.8%)
Elemental Analysis (%) for:C76H56Cu2I2P4:C,61.93；H,3.83.
This experiment obtains the Ultraluminescence spectrum of the multiple tooth double transmitting electroluminescent dyestuff DPACuI of phosphine coordination copper complex, phosphorus
Light spectrum spectrogram is as shown in Figure 1.This experiment obtains the heat of the multiple tooth double transmitting electroluminescent dyestuff DPACuI of phosphine coordination copper complex
Weight analysis spectrogram is as shown in Fig. 2 the cracking of the multiple tooth double transmitting electroluminescent dyestuff DPACuI of phosphine coordination copper complex as seen from the figure
Temperature is 383 DEG C.
The multiple tooth double transmitting electroluminescent dyestuff DPACuI of phosphine coordination copper complex are used to prepare electroluminescent as luminescent layer
The method of device is as follows：
First, the plastic supporting base cleaned through deionized water is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed
Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is the anode conducting of 10nm
Layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material TAPC is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, multiple tooth double transmitting electroluminescent dyestuff and the material of main parts of phosphine coordination copper complex are deposited with hole transmission layer
MCP mixes, and obtains thickness for 15nm；
5th, electron transport layer materials TPBi is deposited with luminescent layer, thickness is 80nm electron transfer layers；
6th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
7th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device
Part.Metal described in step 7 is aluminium.The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/TAPC
(40nm)/mCP:DPACuI(15nm)/TPBi(80nm)/LiF(10nm)/Al.This experiment is double with multiple tooth phosphine coordination copper complex
The voltage-current density relation curve of electroluminescent device prepared by transmitting electroluminescent dyestuff DPACuI is as shown in figure 9, thus
Figure understands that the multiple tooth double transmitting electroluminescent dyestuff DPACuI materials of phosphine coordination copper complex have characteristic of semiconductor, its threshold voltage
It is 3.9V.The electroluminescent device that this experiment is prepared with the double transmitting electroluminescent dyestuff DPACuI of multiple tooth phosphine coordination copper complex
As shown in Figure 10, thus figure understands that the bright voltage that opens of the device is 3.8V to voltage-brightness relation curve.This experiment is matched somebody with somebody with multiple tooth phosphine
The luminance-current efficiency relation curve of electroluminescent device prepared by the double transmitting electroluminescent dyestuff DPACuI of position copper complex is such as
Shown in Figure 11, thus figure understands that the device is 2.4cdm in brightness-2When, current efficiency reaches maximum 17.7cdA-1.This
Test the brightness-power of the electroluminescent device prepared with the double transmitting electroluminescent dyestuff DPACuI of multiple tooth phosphine coordination copper complex
As shown in figure 12, thus figure understands that the device is 2.1cdm in brightness to relationship between efficiency curve-2When, power efficiency reaches maximum
7.7lm·W-1.The electroluminescent cell that this experiment is prepared with the double transmitting electroluminescent dyestuff DPACuI of multiple tooth phosphine coordination copper complex
As shown in figure 13, thus figure understands that the device is 6mAcm in brightness to the current density of part-external quantum efficiency relation curve-2When,
Obtain maximum external quantum efficiency 13.2%.This experiment is with the multiple tooth phosphine double transmitting electroluminescent dyestuff DPACuI systems of coordination copper complex
As shown in figure 14, thus figure understands that the electroluminescent peak of the device exists to the electroluminescent light spectrogram of standby electroluminescent device
At 610nm.As can be seen from Figure 35：As temperature is raised, the life-span drastically declines, and is at low temperature phosphorescent emissions, with the liter of temperature
Height, shows thermal excitation delayed fluorescence property, so as to embody double transmittings.
Experiment four：The synthetic method of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of this experiment follow these steps to
Realize：
The DCM of the multiple tooth Phosphine ligands of 1mmol, CuCl, 5ml of 1mmol is mixed, after 40 DEG C are reacted 10~15 hours, is spin-dried for,
Purified by eluent column chromatography of DCM and PE, obtain multiple tooth phosphine coordination copper complex；
Wherein described multiple tooth Phosphine ligands are 1 ﹕ 1 with the amount ratio of CuCl.
The volume ratio of DCM and PE is 1 ﹕ 20 in described DCM and the mixed solvent of PE.
The multiple tooth phosphine coordination copper complex pair that this experiment is obtained launches electroluminescent Dyes structural formulaes and is
It is PPADPCuCl that this experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex.
The PPADPCuCl modified using the multifunction of Mass Spectrometer Method this experiment preparation, testing result is as follows：
m/z:478.09 (100.0%), 478.59 (64.9%), 479.09 (44.6%), 479.09 (32.0%),
479.59 (28.9%), 479.59 (20.7%), 479.09 (20.7%), 480.08 (14.2%), 480.59 (9.2%),
480.09 (9.2%), 480.09 (6.6%), 479.59 (3.5%), 481.09 (2.9%), 480.59 (1.9%), 480.59
(1.1%).Elemental Analysis (%) for:C60H45ClCuP3:C,75.23；H,4.74.
This experiment obtains the Ultraluminescence light of the multiple tooth double transmitting electroluminescent dyestuff PPADPCuCl of phosphine coordination copper complex
Spectrum, phosphorescence spectrum spectrogram is as shown in Figure 3.This experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex
The thermogravimetric analysis spectrogram of PPADPCuCl launches electroluminescent dyestuffs as shown in figure 4, multiple tooth phosphine coordination copper complex is double as seen from the figure
The cracking temperature of PPADPCuCl is 338 DEG C.
The multiple tooth double transmitting electroluminescent dyestuff PPADPCuCl of phosphine coordination copper complex are used to prepare electroluminescent hair as luminescent layer
The method of optical device is as follows：
First, the plastic supporting base cleaned through deionized water is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed
Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is the anode conducting of 10nm
Layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material TAPC is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, multiple tooth double transmitting electroluminescent dyestuff and the material of main parts of phosphine coordination copper complex are deposited with hole transmission layer
MCP mixes, and obtains thickness for 15nm；
5th, electron transport layer materials TPBi is deposited with luminescent layer, thickness is 80nm electron transfer layers；
6th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
7th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device
Part.Metal described in step 7 is aluminium.The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/TAPC
(40nm)/mCP:PPADPCuCl(15nm)/TPBi(80nm)/LiF(10nm)/Al。
The electroluminescent cell that this experiment is prepared with the double transmitting electroluminescent dyestuff PPADPCuCl of multiple tooth phosphine coordination copper complex
As shown in figure 15, thus figure understands the double electroluminescent hairs of transmitting of multiple tooth phosphine coordination copper complex to the voltage-current density relation curve of part
Photoinitiator dye PPADPCuCl materials have characteristic of semiconductor, and its threshold voltage is 3.9V.This experiment is coordinated copper complex with multiple tooth phosphine
The voltage-brightness relation curve of electroluminescent device prepared by double transmitting electroluminescent dyestuff PPADPCuCl is as shown in figure 16, by
This figure understands that the bright voltage that opens of the device is 4V.This experiment is with the multiple tooth phosphine double transmitting electroluminescent dyestuffs of coordination copper complex
As shown in figure 17, thus figure understands the device to the luminance-current efficiency relation curve of electroluminescent device prepared by PPADPCuCl
It is 2.4cdm in brightness-2When, current efficiency reaches maximum 11.5cdA-1.This experiment is coordinated copper complex with multiple tooth phosphine
Brightness-power efficiency relation curve such as Figure 18 institutes of electroluminescent device prepared by double transmitting electroluminescent dyestuff PPADPCuCl
Show, thus figure understands that the device is 2.1cdm in brightness-2When, power efficiency reaches maximum 60lmW-1.This experiment is with more
The current density of electroluminescent device prepared by the double transmitting electroluminescent dyestuff PPADPCuCl of tooth phosphine coordination copper complex-outer amount
As shown in figure 19, thus figure understands that the device is 6mAcm in brightness to sub- relationship between efficiency curve-2When, obtain maximum outer quantum effect
Rate 22.1%.The electroluminescent that this experiment is prepared with the double transmitting electroluminescent dyestuff PPADPCuCl of multiple tooth phosphine coordination copper complex
As shown in figure 20, thus figure understands the electroluminescent peak of the device at 610nm to the electroluminescent light spectrogram of device.Can from Figure 36
Know：As temperature is raised, the life-span drastically declines, and is at low temperature phosphorescent emissions, with the rising of temperature, shows thermal excitation and prolongs
Slow photoluminescent property, so as to embody double transmittings.
Experiment five：The synthetic method of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of this experiment follow these steps to
Realize：
The DCM of the multiple tooth Phosphine ligands of 1mmol, CuBr, 5ml of 1mmol is mixed, after 40~45 DEG C are reacted 10~15 hours,
It is spin-dried for, is purified by eluent column chromatography of DCM and PE, obtains multiple tooth phosphine coordination copper complex；
Wherein described multiple tooth Phosphine ligands are 1 ﹕ 1 with the amount ratio of CuBr.
The volume ratio of DCM and PE is 1 ﹕ 20 in described DCM and the mixed solvent of PE.
The multiple tooth phosphine coordination copper complex pair that this experiment is obtained launches electroluminescent Dyes structural formulaes and is
It is PPADPCuBr that this experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex.
The PPADPCuBr modified using the multifunction of Mass Spectrometer Method this experiment preparation, testing result is as follows：
m/z:500.06 (100.0%), 501.06 (97.3%), 500.56 (64.9%), 501.56 (63.1%),
501.06 (44.6%), 502.06 (43.4%), 501.56 (28.9%), 502.56 (28.1%), 502.06 (20.1%),
501.06 (15.6%), 502.06 (9.2%), 503.06 (9.0%), 501.06 (5.1%), 502.57 (3.9%), 501.57
(2.7%), 503.56 (1.9%), 501.57 (1.7%), 502.57 (1.2%).Elemental Analysis (%) for
C60H45BrCuP3:C,71.89；H,4.53.
This experiment obtains the Ultraluminescence light of the multiple tooth double transmitting electroluminescent dyestuff PPADPCuBr of phosphine coordination copper complex
Spectrum, phosphorescence spectrum spectrogram is as shown in Figure 3.This experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex
The thermogravimetric analysis spectrogram of PPADPCuBr launches electroluminescent dyestuffs as shown in figure 4, multiple tooth phosphine coordination copper complex is double as seen from the figure
The cracking temperature of PPADPCuBr is 424 DEG C.
The multiple tooth double transmitting electroluminescent dyestuff PPADPCuBr of phosphine coordination copper complex are used to prepare electroluminescent hair as luminescent layer
The method of optical device is as follows：
First, the plastic supporting base cleaned through deionized water is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed
Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is the anode conducting of 10nm
Layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material TAPC is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, multiple tooth double transmitting electroluminescent dyestuff and the material of main parts of phosphine coordination copper complex are deposited with hole transmission layer
MCP mixes, and obtains thickness for 15nm；
5th, electron transport layer materials TPBi is deposited with luminescent layer, thickness is 80nm electron transfer layers；
6th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
7th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device
Part.Metal described in step 7 is aluminium.The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/TAPC
(40nm)/mCP:PPADPCuBr(15nm)/TPBi(80nm)/LiF(10nm)/Al.This experiment is coordinated copper complex with multiple tooth phosphine
Voltage-current density relation curve such as Figure 15 institutes of electroluminescent device prepared by double transmitting electroluminescent dyestuff PPADPCuBr
Show, thus figure understands that the multiple tooth double transmitting electroluminescent dyestuff PPADPCuBr materials of phosphine coordination copper complex have characteristic of semiconductor,
Its threshold voltage is 3.8V.This experiment is prepared with the double transmitting electroluminescent dyestuff PPADPCuBr of multiple tooth phosphine coordination copper complex
As shown in figure 16, thus figure understands that the bright voltage that opens of the device is 3.9V to the voltage-brightness relation curve of electroluminescent device.This
The brightness of the electroluminescent devices that experiment is prepared with the double transmitting electroluminescent dyestuff PPADPCuBr of multiple tooth phosphine coordination copper complex-
As shown in figure 17, thus figure understands that the device is 2.6cdm in brightness to current efficiency relation curve-2When, current efficiency reaches most
Big value 7.8cdA-1.This experiment is electroluminescent with the double transmitting electroluminescent dyestuff PPADPCuBr preparations of multiple tooth phosphine coordination copper complex
As shown in figure 18, thus figure understands that the device is 2.1cdm in brightness to the brightness-power efficiency relation curve of luminescent device-2
When, power efficiency reaches maximum 40lmW-1.This experiment is with the multiple tooth phosphine double transmitting electroluminescent dyestuffs of coordination copper complex
As shown in figure 19, thus figure understands the current density-external quantum efficiency relation curve of electroluminescent device prepared by PPADPCuBr
The device is 6mAcm in brightness-2When, obtain maximum external quantum efficiency 20.5%.This experiment is coordinated copper complex with multiple tooth phosphine
The electroluminescent light spectrogram of electroluminescent device prepared by double transmitting electroluminescent dyestuff PPADPCuBr is as shown in figure 20, thus
Figure understands the electroluminescent peak of the device at 610nm.As can be seen from Figure 37：As temperature is raised, the life-span drastically declines, in low temperature
Under be phosphorescent emissions, with the rising of temperature, thermal excitation delayed fluorescence property is shown, so as to embody double transmittings.
Experiment six：The synthetic method of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of this experiment follow these steps to
Realize：
The DCM of the multiple tooth Phosphine ligands of 1mmol, CuI, 5ml of 1mmol is mixed, after 40~45 DEG C are reacted 10~15 hours, rotation
It is dry, purified by eluent column chromatography of DCM and PE, obtain multiple tooth phosphine coordination copper complex；
Wherein described multiple tooth Phosphine ligands are 1 ﹕ 1 with the amount ratio of CuI.
The volume ratio of DCM and PE is 1 ﹕ 20 in described DCM and the mixed solvent of PE.
The multiple tooth phosphine coordination copper complex pair that this experiment is obtained launches electroluminescent Dyes structural formulaes and is
It is PPADPCuI that this experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex.
The PPADPCuI modified using the multifunction of Mass Spectrometer Method this experiment preparation, testing result is as follows：
m/z:524.05 (100.0%), 524.56 (64.9%), 525.05 (44.6%), 525.56 (28.9%),
525.06 (20.7%), 526.06 (9.2%), 525.56 (3.5%), 526.56 (1.9%).Elemental Analysis
(%) for C60H45CuIP3:C,68.67；H,4.32.
This experiment obtains the Ultraluminescence spectrum of the multiple tooth double transmitting electroluminescent dyestuff PPADPCuI of phosphine coordination copper complex,
Phosphorescence spectrum spectrogram is as shown in Figure 3.This experiment obtains the multiple tooth double transmitting electroluminescent dyestuff PPADPCuI of phosphine coordination copper complex
Thermogravimetric analysis spectrogram as shown in figure 4, double transmitting electroluminescent dyestuff PPADPCuI of multiple tooth phosphine coordination copper complex as seen from the figure
Cracking temperature be 446 DEG C.
The multiple tooth double transmitting electroluminescent dyestuff PPADPCuI of phosphine coordination copper complex are used to prepare electroluminescent hair as luminescent layer
The method of optical device is as follows：
First, the plastic supporting base cleaned through deionized water is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed
Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is the anode conducting of 10nm
Layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material TAPC is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, multiple tooth double transmitting electroluminescent dyestuff and the material of main parts of phosphine coordination copper complex are deposited with hole transmission layer
MCP mixes, and obtains thickness for 15nm；
5th, electron transport layer materials TPBi is deposited with luminescent layer, thickness is 80nm electron transfer layers；
6th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
7th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device
Part.Metal described in step 7 is aluminium.The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/TAPC
(40nm)/mCP:PPADPCuI(15nm)/TPBi(80nm)/LiF(10nm)/Al.This experiment is coordinated copper complex with multiple tooth phosphine
Voltage-current density relation curve such as Figure 15 institutes of electroluminescent device prepared by double transmitting electroluminescent dyestuff PPADPCuI
Show, thus figure understands that the multiple tooth double transmitting electroluminescent dyestuff PPADPCuI materials of phosphine coordination copper complex have characteristic of semiconductor,
Its threshold voltage is 3.7V.The electricity that this experiment is prepared with the double transmitting electroluminescent dyestuff PPADPCuI of multiple tooth phosphine coordination copper complex
As shown in figure 16, thus figure understands that the bright voltage that opens of the device is 3.8V to the voltage-brightness relation curve of electroluminescence device.This reality
Test the luminance-current of the electroluminescent device prepared with the double transmitting electroluminescent dyestuff PPADPCuI of multiple tooth phosphine coordination copper complex
As shown in figure 17, thus figure understands that the device is 2.4cdm in brightness to relationship between efficiency curve-2When, current efficiency reaches maximum
13.2cd·A-1.The electroluminescent that this experiment is prepared with the double transmitting electroluminescent dyestuff PPADPCuI of multiple tooth phosphine coordination copper complex
As shown in figure 18, thus figure understands that the device is 2.1cdm in brightness to the brightness-power efficiency relation curve of device-2When, work(
Rate efficiency reaches maximum 77.7lmW-1.This experiment is with the multiple tooth phosphine double transmitting electroluminescent dyestuffs of coordination copper complex
As shown in figure 19, thus figure understands the current density-external quantum efficiency relation curve of electroluminescent device prepared by PPADPCuI
The device is 6mAcm in brightness-2When, obtain maximum external quantum efficiency 20.1%.This experiment is coordinated copper complex with multiple tooth phosphine
The electroluminescent light spectrogram of electroluminescent device prepared by double transmitting electroluminescent dyestuff PPADPCuI as shown in figure 20, is thus schemed
Understand the electroluminescent peak of the device at 610nm.As can be seen from Figure 38：As temperature is raised, the life-span drastically declines, at low temperature
It is phosphorescent emissions, with the rising of temperature, shows thermal excitation delayed fluorescence property, so as to embodies double transmittings.
Experiment seven：The synthetic method of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of this experiment follow these steps to
Realize：
The DCM of the multiple tooth Phosphine ligands of 1mmol, CuCl, 5ml of 1mmol is mixed, after 40 DEG C are reacted 10~15 hours, is spin-dried for,
Purified by eluent column chromatography of DCM and PE, obtain multiple tooth phosphine coordination copper complex；
Wherein described multiple tooth Phosphine ligands are 1 ﹕ 1 with the amount ratio of CuCl.
The volume ratio of DCM and PE is 1 ﹕ 20 in described DCM and the mixed solvent of PE.
The multiple tooth phosphine coordination copper complex pair that this experiment is obtained launches electroluminescent Dyes structural formulaes and is
It is PPPADPCuCl that this experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex.
The PPPADPCuCl modified using the multifunction of Mass Spectrometer Method this experiment preparation, testing result is as follows：
m/z:461.09 (100.0%), 461.60 (61.6%), 462.09 (44.6%), 462.09 (32.0%),
462.60 (27.5%), 462.59 (19.7%), 462.10 (18.7%), 463.09 (14.2%), 463.59 (8.8%),
463.10 (8.3%), 463.10 (6.0%), 462.60 (2.9%), 464.10 (2.7%), 463.60 (1.7%).
Elemental Analysis (%) for C57H47CuClP3:C,74.10；H,5.13.
This experiment obtains the Ultraluminescence light of the multiple tooth double transmitting electroluminescent dyestuff PPPADPCuCl of phosphine coordination copper complex
Spectrum, phosphorescence spectrum spectrogram is as shown in Figure 5.This experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex
The thermogravimetric analysis spectrogram of PPPADPCuCl launches electroluminescent dye as shown in fig. 6, multiple tooth phosphine coordination copper complex is double as seen from the figure
The cracking temperature for expecting PPPADPCuCl is 425 DEG C.
The multiple tooth double transmitting electroluminescent dyestuff PPPADPCuCl of phosphine coordination copper complex are electroluminescent for preparing as luminescent layer
The method of luminescent device is as follows：
First, the plastic supporting base cleaned through deionized water is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed
Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is the anode conducting of 10nm
Layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material TAPC is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, multiple tooth double transmitting electroluminescent dyestuff and the material of main parts of phosphine coordination copper complex are deposited with hole transmission layer
MCP mixes, and obtains thickness for 15nm；
5th, electron transport layer materials TPBi is deposited with luminescent layer, thickness is 80nm electron transfer layers；
6th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
7th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device
Part.Metal described in step 7 is aluminium.The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/TAPC
(40nm)/mCP:PPPADPCuCl(15nm)/TPBi(80nm)/LiF(10nm)/Al.This experiment is coordinated with multiple tooth phosphine coordination copper
Voltage-current density relation curve such as Figure 21 of electroluminescent device prepared by the double transmitting electroluminescent dyestuff PPPADPCuCl of thing
Shown, thus figure understands that the multiple tooth double transmitting electroluminescent dyestuff PPPADPCuCl materials of phosphine coordination copper complex have semiconductor special
Property, its threshold voltage is 4V.This experiment is prepared with the double transmitting electroluminescent dyestuff PPAPDPCuCl of multiple tooth phosphine coordination copper complex
Electroluminescent device voltage-brightness relation curve as shown in figure 22, what thus figure understood the device opens bright voltage for 4V.This
The brightness of the electroluminescent devices that experiment is prepared with the double transmitting electroluminescent dyestuff PPPADPCuCl of multiple tooth phosphine coordination copper complex-
As shown in figure 23, thus figure understands that the device is 2.4cdm in brightness to current efficiency relation curve-2When, current efficiency reaches most
Big value 11.5cdA-1.The electricity that this experiment is prepared with the double transmitting electroluminescent dyestuff PPPADPCuCl of multiple tooth phosphine coordination copper complex
As shown in figure 24, thus figure understands that the device is 2.1cdm in brightness to the brightness-power efficiency relation curve of electroluminescence device-2
When, power efficiency reaches maximum 62lmW-1.This experiment is with the multiple tooth phosphine double transmitting electroluminescent dyestuffs of coordination copper complex
As shown in figure 25, thus figure can for the current density-external quantum efficiency relation curve of electroluminescent device prepared by PPPADPCuCl
Know that the device is 6mAcm in brightness-2When, obtain maximum external quantum efficiency 13.1%.This experiment is coordinated with multiple tooth phosphine coordination copper
The electroluminescent light spectrogram of electroluminescent device prepared by the double transmitting electroluminescent dyestuff PPPADPCuCl of thing is as shown in figure 26, by
This figure understands the electroluminescent peak of the device at 620nm.As can be seen from Figure 39：As temperature is raised, the life-span drastically declines, low
It is phosphorescent emissions under temperature, with the rising of temperature, shows thermal excitation delayed fluorescence property, so as to embodies double transmittings.
Experiment eight：The synthetic method of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of this experiment follow these steps to
Realize：
The DCM of the multiple tooth Phosphine ligands of 1mmol, CuBr, 5ml of 1mmol is mixed, after 40~45 DEG C are reacted 10~15 hours,
It is spin-dried for, is purified by eluent column chromatography of DCM and PE, obtains multiple tooth phosphine coordination copper complex；
Wherein described multiple tooth Phosphine ligands are 1 ﹕ 1 with the amount ratio of CuBr.
The volume ratio of DCM and PE is 1 ﹕ 20 in described DCM and the mixed solvent of PE.
The multiple tooth phosphine coordination copper complex pair that this experiment is obtained launches electroluminescent Dyes structural formulaes and is
It is PPPADPCuBr that this experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex.
The PPPADPCuBr modified using the multifunction of Mass Spectrometer Method this experiment preparation, testing result is as follows：
m/z:483.07 (100.0%), 484.07 (97.3%), 483.57 (61.6%), 484.57 (60.0%),
484.07 (44.6%), 485.07 (43.4%), 484.57 (27.5%), 485.57 (26.7%), 485.07 (18.2%),
484.07 (13.6%), 485.07 (8.3%), 486.07 (8.1%), 484.07 (5.1%), 484.57 (3.7%), 485.57
(3.3%), 486.57 (1.6%)
Elemental Analysis (%) for C57H47CuBrP3:C,70.70；H,4.89.
This experiment obtains the Ultraluminescence light of the multiple tooth double transmitting electroluminescent dyestuff PPPADPCuBr of phosphine coordination copper complex
Spectrum, phosphorescence spectrum spectrogram is as shown in Figure 5.This experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex
The thermogravimetric analysis spectrogram of PPPADPCuBr launches electroluminescent dye as shown in fig. 6, multiple tooth phosphine coordination copper complex is double as seen from the figure
The cracking temperature for expecting PPPADPCuBr is 433 DEG C.
The multiple tooth double transmitting electroluminescent dyestuff PPPADPCuBr of phosphine coordination copper complex are electroluminescent for preparing as luminescent layer
The method of luminescent device is as follows：
First, the plastic supporting base cleaned through deionized water is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed
Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is the anode conducting of 10nm
Layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material TAPC is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, multiple tooth double transmitting electroluminescent dyestuff and the material of main parts of phosphine coordination copper complex are deposited with hole transmission layer
MCP mixes, and obtains thickness for 15nm；
5th, electron transport layer materials TPBi is deposited with luminescent layer, thickness is 80nm electron transfer layers；
6th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
7th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device
Part.Metal described in step 7 is aluminium.The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/TAPC
(40nm)/mCP:PPPADPCuBr(15nm)/TPBi(80nm)/LiF(10nm)/Al.This experiment is coordinated with multiple tooth phosphine coordination copper
Voltage-current density relation curve such as Figure 21 of electroluminescent device prepared by the double transmitting electroluminescent dyestuff PPPADPCuBr of thing
Shown, thus figure understands that the multiple tooth double transmitting electroluminescent dyestuff PPPADPCuBr materials of phosphine coordination copper complex have semiconductor special
Property, its threshold voltage is 6V.This experiment is prepared with the double transmitting electroluminescent dyestuff PPPADPCuBr of multiple tooth phosphine coordination copper complex
Electroluminescent device voltage-brightness relation curve as shown in figure 22, what thus figure understood the device opens bright voltage for 3.9V.
This experiment is bright with the electroluminescent device of the double transmitting electroluminescent dyestuff PPPADPCuBr preparations of multiple tooth phosphine coordination copper complex
As shown in figure 23, thus figure understands that the device is 2.6cdm in brightness to degree-current efficiency relation curve-2When, current efficiency reaches
To maximum 11.8cdA-1.This experiment is prepared with the double transmitting electroluminescent dyestuff PPPADPCuBr of multiple tooth phosphine coordination copper complex
Electroluminescent device brightness-power efficiency relation curve as shown in figure 24, thus figure understand the device be in brightness
2.1cd·m-2When, power efficiency reaches maximum 65lmW-1.This experiment is electroluminescent with the double transmittings of coordination copper complex of multiple tooth phosphine
Current density-external quantum efficiency the relation curve of electroluminescent device prepared by luminescent dye PPPADPCuBr is as shown in figure 25,
Thus figure understands that the device is 6mAcm in brightness-2When, obtain maximum external quantum efficiency 14.5%.This experiment is matched somebody with somebody with multiple tooth phosphine
The electroluminescent light spectrogram of electroluminescent device prepared by the double transmitting electroluminescent dyestuff PPPADPCuBr of position copper complex is as schemed
Shown in 26, thus figure understands the electroluminescent peak of the device at 620nm.As can be seen from Figure 40：As temperature is raised, the life-span is drastically
Decline, be at low temperature phosphorescent emissions, with the rising of temperature, show thermal excitation delayed fluorescence property, it is double so as to embody
Transmitting.
Experiment nine：The synthetic method of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of this experiment follow these steps to
Realize：
The DCM of the multiple tooth Phosphine ligands of 1mmol, CuI, 5ml of 1mmol is mixed, after 40~45 DEG C are reacted 10~15 hours, rotation
It is dry, purified by eluent column chromatography of DCM and PE, obtain multiple tooth phosphine coordination copper complex；
Wherein described multiple tooth Phosphine ligands are 1 ﹕ 1 with the amount ratio of CuI.
The volume ratio of DCM and PE is 1 ﹕ 20 in described DCM and the mixed solvent of PE.
The multiple tooth phosphine coordination copper complex pair that this experiment is obtained launches electroluminescent Dyes structural formulaes and is
It is PPPADPCuI that this experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex.
The PPPACuI modified using the multifunction of Mass Spectrometer Method this experiment preparation, testing result is as follows：
m/z:507.06 (100.0%), 507.56 (61.6%), 508.06 (44.6%), 508.56 (27.5%),
508.07 (18.7%), 509.06 (8.3%), 508.57 (2.9%), 509.57 (1.7%).Elemental Analysis
(%) for C57H47CuIP3:C,67.43；H,4.67；Cu,6.26；I,12.50；P,9.15.
This experiment obtains the Ultraluminescence light of the multiple tooth double transmitting electroluminescent dyestuff PPPADPCuI of phosphine coordination copper complex
Spectrum, phosphorescence spectrum spectrogram is as shown in Figure 5.This experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex
The thermogravimetric analysis spectrogram of PPPADPCuI launches electroluminescent dyestuffs as shown in fig. 6, multiple tooth phosphine coordination copper complex is double as seen from the figure
The cracking temperature of PPPADPCuI is 437 DEG C.
The multiple tooth double transmitting electroluminescent dyestuff PPPADPCuI of phosphine coordination copper complex are used to prepare electroluminescent hair as luminescent layer
The method of optical device is as follows：
First, the plastic supporting base cleaned through deionized water is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed
Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is the anode conducting of 10nm
Layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material TAPC is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, multiple tooth double transmitting electroluminescent dyestuff and the material of main parts of phosphine coordination copper complex are deposited with hole transmission layer
MCP mixes, and obtains thickness for 15nm；
5th, electron transport layer materials TPBi is deposited with luminescent layer, thickness is 80nm electron transfer layers；
6th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
7th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device
Part.Metal described in step 7 is aluminium.The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/TAPC
(40nm)/mCP:PPPADPCuI(15nm)/TPBi(80nm)/LiF(10nm)/Al.This experiment is coordinated copper complex with multiple tooth phosphine
Voltage-current density relation curve such as Figure 21 institutes of electroluminescent device prepared by double transmitting electroluminescent dyestuff PPPADPCuI
Show, thus figure understands that the multiple tooth double transmitting electroluminescent dyestuff PPPADPCuI materials of phosphine coordination copper complex have characteristic of semiconductor,
Its threshold voltage is 6V.The electricity that this experiment is prepared with the double transmitting electroluminescent dyestuff PPPADPCuI of multiple tooth phosphine coordination copper complex
As shown in figure 22, thus figure understands that the bright voltage that opens of the device is 3.8V to the voltage-brightness relation curve of electroluminescence device.This reality
Test the brightness-electricity of the electroluminescent device prepared with the double transmitting electroluminescent dyestuff PPPADPCuI of multiple tooth phosphine coordination copper complex
As shown in figure 23, thus figure understands that the device is 2.4cdm in brightness to stream relationship between efficiency curve-2When, current efficiency reaches maximum
Value 18cdA-1.The electroluminescent hair that this experiment is prepared with the double transmitting electroluminescent dyestuff PPPADPCuI of multiple tooth phosphine coordination copper complex
As shown in figure 24, thus figure understands that the device is 2.1cdm in brightness to the brightness-power efficiency relation curve of optical device-2When,
Power efficiency reaches maximum 70.7lmW-1.This experiment is with the multiple tooth phosphine double transmitting electroluminescent dyestuffs of coordination copper complex
As shown in figure 25, thus figure understands the current density-external quantum efficiency relation curve of electroluminescent device prepared by PPPADPCuI
The device is 6mAcm in brightness-2When, obtain maximum external quantum efficiency 14.2%.This experiment is coordinated copper complex with multiple tooth phosphine
The electroluminescent light spectrogram of electroluminescent device prepared by double transmitting electroluminescent dyestuff PPPADPCuI is as shown in figure 26, thus
Figure understands that is as can be seen from Figure 41 at 621nm for the electroluminescent peak of the device：As temperature is raised, the life-span drastically declines, in low temperature
Under be phosphorescent emissions, with the rising of temperature, thermal excitation delayed fluorescence property is shown, so as to embody double transmittings.
Experiment ten：The synthetic method of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of this experiment follow these steps to
Realize：
The DCM of the multiple tooth Phosphine ligands of 1mmol, CuCl, 5ml of 1mmol is mixed, after 40 DEG C are reacted 10~15 hours, is spin-dried for,
Purified by eluent column chromatography of DCM and PE, obtain multiple tooth phosphine coordination copper complex；
Wherein described multiple tooth Phosphine ligands are 1 ﹕ 1 with the amount ratio of CuCl.
The volume ratio of DCM and PE is 1 ﹕ 20 in described DCM and the mixed solvent of PE.
The multiple tooth phosphine coordination copper complex pair that this experiment is obtained launches electroluminescent Dyes structural formulaes and is
It is DPAPCuCl that this experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex.
The DPAPCuCl modified using the multifunction of Mass Spectrometer Method this experiment preparation, testing result is as follows：
m/z:620.12 (100.0%), 620.63 (86.5%), 621.12 (44.6%), 621.62 (38.6%),
621.13 (37.0%), 621.12 (32.0%), 621.62 (27.7%), 622.13 (16.5%), 622.12 (14.2%),
622.62 (12.3%), 622.13 (11.8%), 621.63 (10.4%), 623.13 (5.3%), 622.63 (4.6%),
622.63 (3.1%), 622.13 (1.8%), 623.63 (1.4%).Elemental Analysis (%) for
C80H58CuClP4:C,77.35；H,4.71.
This experiment obtains the Ultraluminescence spectrum of the multiple tooth double transmitting electroluminescent dyestuff DPAPCuCl of phosphine coordination copper complex,
Phosphorescence spectrum spectrogram is as shown in Figure 7.This experiment obtains the multiple tooth double transmitting electroluminescent dyestuff DPAPCuCl of phosphine coordination copper complex
Thermogravimetric analysis spectrogram as shown in figure 8, double transmitting electroluminescent dyestuff DPAPCuCl of multiple tooth phosphine coordination copper complex as seen from the figure
Cracking temperature be 421 DEG C.
The multiple tooth double transmitting electroluminescent dyestuff DPAPCuCl of phosphine coordination copper complex are used to prepare electroluminescent hair as luminescent layer
The method of optical device is as follows：
First, the plastic supporting base cleaned through deionized water is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed
Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is the anode conducting of 10nm
Layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material TAPC is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, multiple tooth double transmitting electroluminescent dyestuff and the material of main parts of phosphine coordination copper complex are deposited with hole transmission layer
MCP mixes, and obtains thickness for 15nm；
5th, electron transport layer materials TPBi is deposited with luminescent layer, thickness is 80nm electron transfer layers；
6th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
7th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device
Part.Metal described in step 7 is aluminium.The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/TAPC
(40nm)/mCP:DPAPCuCl(15nm)/TPBi(80nm)/LiF(10nm)/Al.This experiment is coordinated copper complex with multiple tooth phosphine
Voltage-current density relation curve such as Figure 27 institutes of electroluminescent device prepared by double transmitting electroluminescent dyestuff DPAPCuCl
Show, thus figure understands that the multiple tooth double transmitting electroluminescent dyestuff DPAPCuCl materials of phosphine coordination copper complex have characteristic of semiconductor,
Its threshold voltage is 3.9V.The electricity that this experiment is prepared with the double transmitting electroluminescent dyestuff DPAPCuCl of multiple tooth phosphine coordination copper complex
As shown in figure 28, thus figure understands that the bright voltage that opens of the device is 4V to the voltage-brightness relation curve of electroluminescence device.This experiment
The luminance-current of the electroluminescent device prepared with the double transmitting electroluminescent dyestuff DPAPCuCl of multiple tooth phosphine coordination copper complex is imitated
As shown in figure 29, thus figure understands that the device is 2.4cdm in brightness to rate relation curve-2When, current efficiency reaches maximum
16.7cd·A-1.The electroluminescent that this experiment is prepared with the double transmitting electroluminescent dyestuff DPAPCuCl of multiple tooth phosphine coordination copper complex
Shown in the brightness of device-power efficiency relation curve Figure 30, thus figure understands that the device is 2.1cdm in brightness-2When, power
Efficiency reaches maximum 10lmW-1.This experiment is with the multiple tooth phosphine double transmitting electroluminescent dyestuff DPAPCuCl systems of coordination copper complex
As shown in figure 31, thus figure understands the device bright to the current density of standby electroluminescent device-external quantum efficiency relation curve
It is 6mAcm to spend-2When, obtain maximum external quantum efficiency 15.3%.This experiment is electroluminescent with the double transmittings of coordination copper complex of multiple tooth phosphine
As shown in figure 32, thus figure understands the device to the electroluminescent light spectrogram of electroluminescent device prepared by luminescent dye DPAPCuCl
Electroluminescent peak at 621nm.As can be seen from Figure 42：As temperature is raised, the life-span drastically declines, and is at low temperature phosphorescence hair
Penetrate, with the rising of temperature, show thermal excitation delayed fluorescence property, so as to embody double transmittings.
Test 11：The synthetic method of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of this experiment presses following step
It is rapid to realize：
The DCM of the multiple tooth Phosphine ligands of 1mmol, CuBr, 5ml of 1mmol is mixed, after 40~45 DEG C are reacted 10~15 hours,
It is spin-dried for, is purified by eluent column chromatography of DCM and PE, obtains multiple tooth phosphine coordination copper complex；
Wherein described multiple tooth Phosphine ligands are 1 ﹕ 1 with the amount ratio of CuBr.
The volume ratio of DCM and PE is 1 ﹕ 20 in described DCM and the mixed solvent of PE.
The multiple tooth phosphine coordination copper complex pair that this experiment is obtained launches electroluminescent Dyes structural formulaes and is
It is DPAPCuBr that this experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex.
The DPAPCuBr modified using the multifunction of Mass Spectrometer Method this experiment preparation, testing result is as follows：
m/z:642.10 (100.0%), 643.10 (97.3%), 642.60 (85.4%), 643.60 (84.2%),
643.10 (44.6%), 644.10 (43.4%), 643.60 (38.6%), 644.60 (37.5%), 644.10 (35.1%),
643.10 (30.0%), 645.10 (15.6%), 644.10 (13.4%), 643.60 (10.3%), 644.60 (9.0%),
643.10 (6.9%), 644.60 (4.6%), 645.60 (4.5%), 644.10 (3.1%), 644.11 (2.2%), 645.10
(2.1%), 642.60 (1.1%), 644.60 (1.1%)
Elemental Analysis (%) for C80H58CuBrP4:C,74.68；H,4.54；Br,6.21；Cu,4.94；
P,9.63。
This experiment obtains the Ultraluminescence spectrum of the multiple tooth double transmitting electroluminescent dyestuff DPAPCuBr of phosphine coordination copper complex,
Phosphorescence spectrum spectrogram is as shown in Figure 7.This experiment obtains the multiple tooth double transmitting electroluminescent dyestuff DPAPCuBr of phosphine coordination copper complex
Thermogravimetric analysis spectrogram as shown in figure 8, double transmitting electroluminescent dyestuff DPAPCuBr of multiple tooth phosphine coordination copper complex as seen from the figure
Cracking temperature be 419 DEG C.
The multiple tooth double transmitting electroluminescent dyestuff DPAPCuBr of phosphine coordination copper complex are used to prepare electroluminescent hair as luminescent layer
The method of optical device is as follows：
First, the plastic supporting base cleaned through deionized water is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed
Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is the anode conducting of 10nm
Layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material TAPC is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, multiple tooth double transmitting electroluminescent dyestuff and the material of main parts of phosphine coordination copper complex are deposited with hole transmission layer
MCP mixes, and obtains thickness for 15nm；
5th, electron transport layer materials TPBi is deposited with luminescent layer, thickness is 80nm electron transfer layers；
6th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
7th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device
Part.Metal described in step 7 is aluminium.The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/TAPC
(40nm)/mCP:DPAPCuBr(15nm)/TPBi(80nm)/LiF(10nm)/Al.This experiment is coordinated copper complex with multiple tooth phosphine
Voltage-current density relation curve such as Figure 27 institutes of electroluminescent device prepared by double transmitting electroluminescent dyestuff DPAPCuBr
Show, thus figure understands that the multiple tooth double transmitting electroluminescent dyestuff DPAPCuBr materials of phosphine coordination copper complex have characteristic of semiconductor,
Its threshold voltage is 3.8V.The electricity that this experiment is prepared with the double transmitting electroluminescent dyestuff DPAPCuBr of multiple tooth phosphine coordination copper complex
As shown in figure 28, thus figure understands that the bright voltage that opens of the device is 3.9V to the voltage-brightness relation curve of electroluminescence device.This reality
Test the luminance-current of the electroluminescent device prepared with the double transmitting electroluminescent dyestuff DPAPCuBr of multiple tooth phosphine coordination copper complex
As shown in figure 29, thus figure understands that the device is 2.6cdm in brightness to relationship between efficiency curve-2When, current efficiency reaches maximum
16.1cd·A-1.The electroluminescent that this experiment is prepared with the double transmitting electroluminescent dyestuff DPAPCuBr of multiple tooth phosphine coordination copper complex
As shown in figure 30, thus figure understands that the device is 2.1cdm in brightness to the brightness-power efficiency relation curve of device-2When, work(
Rate efficiency reaches maximum 12.6lmW-1.This experiment is with the multiple tooth phosphine double transmitting electroluminescent dyestuffs of coordination copper complex
As shown in figure 31, thus figure understands the current density-external quantum efficiency relation curve of electroluminescent device prepared by DPAPCuBr
The device is 6mAcm in brightness-2When, obtain maximum external quantum efficiency 15.4%.This experiment is coordinated copper complex with multiple tooth phosphine
The electroluminescent light spectrogram of electroluminescent device prepared by double transmitting electroluminescent dyestuff DPAPCuBr as shown in figure 32, is thus schemed
Understand the electroluminescent peak of the device at 621nm.As can be seen from Figure 43：As temperature is raised, the life-span drastically declines, at low temperature
It is phosphorescent emissions, with the rising of temperature, shows thermal excitation delayed fluorescence property, so as to embodies double transmittings.
Test 12：The synthetic method of the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex of this experiment presses following step
It is rapid to realize：
The DCM of the multiple tooth Phosphine ligands of 1mmol, CuI, 5ml of 1mmol is mixed, after 40~45 DEG C are reacted 10~15 hours, rotation
It is dry, purified by eluent column chromatography of DCM and PE, obtain multiple tooth phosphine coordination copper complex；
Wherein described multiple tooth Phosphine ligands are 1 ﹕ 1 with the amount ratio of CuI.
The volume ratio of DCM and PE is 1 ﹕ 20 in described DCM and the mixed solvent of PE.
The multiple tooth phosphine coordination copper complex pair that this experiment is obtained launches electroluminescent Dyes structural formulaes and is
It is DPAPCuI that this experiment obtains the multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex.
The DPAPCuI modified using the multifunction of Mass Spectrometer Method this experiment preparation, testing result is as follows：
m/z:666.09 (100.0%), 666.59 (86.5%), 667.09 (44.6%), 667.59 (38.6%),
667.10 (37.0%), 668.09 (16.5%), 667.60 (10.4%), 668.60 (4.6%), 668.10 (1.8%)
Elemental Analysis (%) for C80H58CuIP4:C,72.05；H,4.38.
This experiment obtains the Ultraluminescence spectrum of the multiple tooth double transmitting electroluminescent dyestuff DPAPCuI of phosphine coordination copper complex,
Phosphorescence spectrum spectrogram is as shown in Figure 7.This experiment obtains the multiple tooth double transmitting electroluminescent dyestuff DPAPCuI's of phosphine coordination copper complex
Thermogravimetric analysis spectrogram is as shown in figure 8, the cracking of the multiple tooth double transmitting electroluminescent dyestuff DPAP of phosphine coordination copper complex as seen from the figure
Temperature is 423 DEG C.
The multiple tooth double transmitting electroluminescent dyestuff DPAPCuI of phosphine coordination copper complex are used to prepare electroluminescent as luminescent layer
The method of device is as follows：
First, the plastic supporting base cleaned through deionized water is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation speed
Rate is set to 0.1nm s-1, deposition material is tin indium oxide (ITO) on glass or plastic supporting base, and thickness is the anode conducting of 10nm
Layer；
2nd, hole injection layer material MoOx is deposited with anode conductive layer, thickness is obtained for 10nm hole injection layers；
3rd, hole transport layer material TAPC is deposited with hole injection layer, thickness is obtained for 40nm hole transmission layers；
4th, multiple tooth double transmitting electroluminescent dyestuff and the material of main parts of phosphine coordination copper complex are deposited with hole transmission layer
MCP mixes, and obtains thickness for 15nm；
5th, electron transport layer materials TPBi is deposited with luminescent layer, thickness is 80nm electron transfer layers；
6th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 10nm electron injecting layers；
7th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 10nm, obtains electroluminescent phosphorescence device
Part.Metal described in step 7 is aluminium.The structure of this experiment electro phosphorescent device is：ITO/MoOx(10nm)/TAPC
(40nm)/mCP:DPAPCuI(15nm)/TPBi(80nm)/LiF(10nm)/Al.This experiment is double with multiple tooth phosphine coordination copper complex
The voltage-current density relation curve of electroluminescent device prepared by transmitting electroluminescent dyestuff DPAPCuI is as shown in figure 27, by
This figure understands that the multiple tooth double transmitting electroluminescent dyestuff DPAPCuI materials of phosphine coordination copper complex have characteristic of semiconductor, its threshold values
Voltage is 3.9V.The electroluminescent that this experiment is prepared with the double transmitting electroluminescent dyestuff DPAPCuI of multiple tooth phosphine coordination copper complex
As shown in figure 28, thus figure understands that the bright voltage that opens of the device is 3.9V to the voltage-brightness relation curve of device.This experiment is with more
The luminance-current efficiency of electroluminescent device prepared by the double transmitting electroluminescent dyestuff DPAPCuI of tooth phosphine coordination copper complex is closed
It is that curve schemes to understand that the device is 2.4cdm in brightness as shown in figure 29, thus-2When, current efficiency reaches maximum
15.7cd·A-1.The electroluminescent that this experiment is prepared with the double transmitting electroluminescent dyestuff DPAPCuI of multiple tooth phosphine coordination copper complex
As shown in figure 30, thus figure understands that the device is 2.1cdm in brightness to the brightness-power efficiency relation curve of device-2When, work(
Rate efficiency reaches maximum 10lmW-1.This experiment is with the double transmitting electroluminescent dyestuff DPAPCuI of multiple tooth phosphine coordination copper complex
As shown in figure 31, thus figure understands that the device exists to the current density of the electroluminescent device of preparation-external quantum efficiency relation curve
Brightness is 6mAcm-2When, obtain maximum external quantum efficiency 15%.This experiment is electroluminescent with the double transmittings of coordination copper complex of multiple tooth phosphine
As shown in figure 32, thus figure understands the device to the electroluminescent light spectrogram of electroluminescent device prepared by luminescent dye DPAPCuI
Electroluminescent peak at 621nm.As can be seen from Figure 44：As temperature is raised, the life-span drastically declines, and is at low temperature phosphorescence hair
Penetrate, with the rising of temperature, show thermal excitation delayed fluorescence property, so as to embody double transmittings.
Claims (11)
1. multiple tooth phosphine coordination copper complex is double launches electroluminescent dyestuffs, it is characterised in that the dyestuff is with multiple tooth Phosphine ligands and CuX
Coordination is constituted, and molecular structural formula is as follows：
The multiple tooth Phosphine ligands are DPA, PPADP, PPPADP or DPAP, and wherein X is Cl, Br or I.
2. multiple tooth phosphine coordination copper complex is double described in claim 1 launches electroluminescent Dyestuff synthesis methods, it is characterised in that should
Synthetic method is as follows：
The dichloromethane of the multiple tooth Phosphine ligands of 1mmol, the CuX of 0.5~1mmol, 5~10ml is mixed, 40-45 DEG C of reaction 10~15
After hour, it is spin-dried for, is purified as eluent column chromatography with dichloromethane and petroleum ether, obtains multiple tooth phosphine coordination copper complex；
The multiple tooth Phosphine ligands are DPA, PPADP, PPPADP or DPAP, and wherein X is Cl, Br or I.
3. multiple tooth phosphine coordination copper complex is double according to claim 2 launches electroluminescent Dyestuff synthesis methods, and its feature exists
In the amount ratio of described multiple tooth Phosphine ligands and the material of CuX be (1~2) ﹕ 1.
4. multiple tooth phosphine coordination copper complex is double according to claim 2 launches electroluminescent Dyestuff synthesis methods, and its feature exists
In the amount ratio of described multiple tooth Phosphine ligands and the material of CuX be 1 ﹕ 1.
5. multiple tooth phosphine coordination copper complex is double according to claim 2 launches electroluminescent Dyestuff synthesis methods, and its feature exists
The volume ratio of DCM and PE is 1 ﹕ 20 in the mixed solvent of described DCM and PE.
6. multiple tooth phosphine coordination copper complex is double according to claim 2 launches electroluminescent Dyestuff synthesis methods, and its feature exists
Reacted 11 hours in 41 DEG C.
7. multiple tooth phosphine coordination copper complex is double according to claim 2 launches electroluminescent Dyestuff synthesis methods, and its feature exists
Reacted 12 hours in 42 DEG C.
8. multiple tooth phosphine coordination copper complex is double according to claim 2 launches electroluminescent Dyestuff synthesis methods, and its feature exists
Reacted 13 hours in 43 DEG C.
9. multiple tooth phosphine coordination copper complex is double according to claim 2 launches electroluminescent Dyestuff synthesis methods, and its feature exists
Reacted 14 hours in 44 DEG C.
10. multiple tooth phosphine coordination copper complex is double according to claim 2 launches electroluminescent Dyestuff synthesis methods, and its feature exists
Reacted 15 hours in 45 DEG C.
The multiple tooth double transmitting electroluminescent applications of phosphine coordination copper complex described in 11. claims 1, it is characterised in that described many
The double transmitting electroluminescent dyestuffs of tooth phosphine coordination copper complex are used to prepare electroluminescent device as the guest materials of luminescent layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710078381.9A CN106749400B (en) | 2017-02-14 | 2017-02-14 | Multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye, and synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710078381.9A CN106749400B (en) | 2017-02-14 | 2017-02-14 | Multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye, and synthesis method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106749400A true CN106749400A (en) | 2017-05-31 |
| CN106749400B CN106749400B (en) | 2021-05-14 |
Family
ID=58956888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710078381.9A Active CN106749400B (en) | 2017-02-14 | 2017-02-14 | Multidentate phosphine-coordinated copper complex dual-emission electroluminescent dye, and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106749400B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997382A (en) * | 2018-06-29 | 2018-12-14 | 湖北大学 | Cuprous halide complex and its synthetic method and application containing thioxene bidentate phosphine ligands |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201249850A (en) * | 2011-04-22 | 2012-12-16 | Sumitomo Chemical Co | Copper complex |
| US20160359126A1 (en) * | 2015-04-30 | 2016-12-08 | Samsung Display Co., Ltd. | Organometallic compound and organic light-emitting device including the same |
-
2017
- 2017-02-14 CN CN201710078381.9A patent/CN106749400B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201249850A (en) * | 2011-04-22 | 2012-12-16 | Sumitomo Chemical Co | Copper complex |
| US20160359126A1 (en) * | 2015-04-30 | 2016-12-08 | Samsung Display Co., Ltd. | Organometallic compound and organic light-emitting device including the same |
Non-Patent Citations (2)
| Title |
|---|
| AKIRA TSUBOYAMA ET AL.: "Photophysical Properties of Highly Luminescent Copper(I) Halide Complexes Chelated with 1,2-Bis(diphenylphosphino)benzene", 《INORGANIC CHEMISTRY》 * |
| ZHANG, JING ET AL.: "Balanced Dual Emissions from Tridentate Phosphine-Coordinate Copper(I) Complexes toward Highly Efficient Yellow OLEDs", 《 ADVANCED MATERIALS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997382A (en) * | 2018-06-29 | 2018-12-14 | 湖北大学 | Cuprous halide complex and its synthetic method and application containing thioxene bidentate phosphine ligands |
| CN108997382B (en) * | 2018-06-29 | 2020-09-29 | 湖北大学 | Cuprous halide complex containing dimethylthiophene bidentate phosphine ligand and synthetic method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106749400B (en) | 2021-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101055923B (en) | Organic electroluminescence device and method for fabricating the same | |
| Sasabe et al. | High‐efficiency blue and white organic light‐emitting devices incorporating a blue iridium carbene complex | |
| CN100459216C (en) | Organic electroluminescent white light device with multi-luminescent layer | |
| CN104393181B (en) | Red organic electroluminescent device and preparation method thereof | |
| CN105601613B (en) | Space charge transfer compounds and the Organic Light Emitting Diode and display device for using the compound | |
| Li et al. | Highly efficient single-and multi-emission-layer fluorescent/phosphorescent hybrid white organic light-emitting diodes with∼ 20% external quantum efficiency | |
| CN106664768B (en) | Organic electroluminescent device and lighting device | |
| CN102185112A (en) | Laminated organic light-emitting diode and preparation method thereof | |
| Cui et al. | High performance red phosphorescent organic electroluminescent devices with characteristic mechanisms by utilizing terbium or gadolinium complexes as sensitizers | |
| CN101384112A (en) | Red organic electroluminescent device and preparation thereof | |
| CN110115107A (en) | Organic electroluminescence device, lighting device and display device | |
| CN108832008A (en) | Application of the exciplex in Organic Light Emitting Diode | |
| Zhou et al. | Double light-emitting layer implementing three-color emission: Using DCJTB lightly doping in Alq3 as red-green emitting layer and APEAn1N as blue-green emitting layer | |
| CN108565346A (en) | A kind of double-colored full fluorescence white light OLED device | |
| CN107452887A (en) | A kind of fluorescent/phosphorescent mixed white light OLED | |
| CN107425137A (en) | A kind of white light OLED device of high color rendering index (CRI) | |
| US20220278293A1 (en) | Organic electroluminescent device and array substrate | |
| CN108682748A (en) | A kind of series connection white light organic electroluminescent device | |
| CN106749400A (en) | The multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex, synthetic method and its application | |
| CN105609653A (en) | White-light OLED device and preparation method thereof | |
| Chen et al. | High-quality all-fluorescent white organic light-emitting diodes obtained by balancing carriers with hole limit layer | |
| CN106866731A (en) | The multiple tooth double transmitting electroluminescent dyestuffs of phosphine coordination copper complex, synthetic method and its application | |
| CN111416047B (en) | Fluorescence/phosphorescence mixed white light organic light emitting diode and preparation method thereof | |
| Ide et al. | High-performance OLEDs and their application to lighting | |
| Chen et al. | Perovskite‐Organic Coupling WLED: Progress and Perspective |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |