CN106831865A - A kind of double phosphine copper cluster electroluminescent materials of feature based on dibenzothiophenes group and preparation method and application - Google Patents
A kind of double phosphine copper cluster electroluminescent materials of feature based on dibenzothiophenes group and preparation method and application Download PDFInfo
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- CN106831865A CN106831865A CN201710081637.1A CN201710081637A CN106831865A CN 106831865 A CN106831865 A CN 106831865A CN 201710081637 A CN201710081637 A CN 201710081637A CN 106831865 A CN106831865 A CN 106831865A
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- dibenzothiophenes group
- feature based
- double phosphine
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- 239000000463 material Substances 0.000 title claims abstract description 301
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical group C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- RRMIKQFUEXQAQP-UHFFFAOYSA-N copper;phosphane Chemical compound P.[Cu] RRMIKQFUEXQAQP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 153
- 239000003446 ligand Substances 0.000 claims abstract description 44
- 150000004820 halides Chemical class 0.000 claims abstract description 40
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003208 petroleum Substances 0.000 claims abstract description 12
- 238000004440 column chromatography Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000003480 eluent Substances 0.000 claims abstract description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 371
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 192
- 235000011150 stannous chloride Nutrition 0.000 claims description 68
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 65
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 65
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 62
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 62
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 62
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 62
- 239000001119 stannous chloride Substances 0.000 claims description 62
- 239000010949 copper Substances 0.000 claims description 41
- 238000005401 electroluminescence Methods 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 210000004209 hair Anatomy 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 228
- 238000000034 method Methods 0.000 abstract description 56
- 238000010521 absorption reaction Methods 0.000 abstract description 40
- 238000004020 luminiscence type Methods 0.000 abstract description 5
- 238000005424 photoluminescence Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000010791 quenching Methods 0.000 abstract description 2
- 230000000171 quenching effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 104
- -1 phosphines iodate Chemical class 0.000 description 74
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 54
- JUGOBHXSAAAXSI-UHFFFAOYSA-N C1=CC=CC=2SC3=C(C21)C=CC=C3.C3=CC=CC=2C1=CC=CC=C1NC32 Chemical group C1=CC=CC=2SC3=C(C21)C=CC=C3.C3=CC=CC=2C1=CC=CC=C1NC32 JUGOBHXSAAAXSI-UHFFFAOYSA-N 0.000 description 50
- 230000009102 absorption Effects 0.000 description 36
- 238000001228 spectrum Methods 0.000 description 34
- 238000002474 experimental method Methods 0.000 description 28
- 230000008859 change Effects 0.000 description 27
- 238000001194 electroluminescence spectrum Methods 0.000 description 27
- 238000000921 elemental analysis Methods 0.000 description 27
- 230000003595 spectral effect Effects 0.000 description 26
- 150000003003 phosphines Chemical class 0.000 description 23
- 238000000862 absorption spectrum Methods 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 18
- ULNVTMFBEVVUMH-UHFFFAOYSA-N P.[Cl] Chemical compound P.[Cl] ULNVTMFBEVVUMH-UHFFFAOYSA-N 0.000 description 13
- DIHZKHJDWYVEEE-UHFFFAOYSA-N P.[Br] Chemical class P.[Br] DIHZKHJDWYVEEE-UHFFFAOYSA-N 0.000 description 12
- 230000004888 barrier function Effects 0.000 description 11
- HSIFENZOKCJPNG-UHFFFAOYSA-N [I].P Chemical compound [I].P HSIFENZOKCJPNG-UHFFFAOYSA-N 0.000 description 10
- 230000005611 electricity Effects 0.000 description 10
- 238000005660 chlorination reaction Methods 0.000 description 9
- 0 Cc(cc1C2CC2)cc2c1SC1C(*)=CC(*)=C=C21 Chemical compound Cc(cc1C2CC2)cc2c1SC1C(*)=CC(*)=C=C21 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- RRLCRPBPKLRKMD-UHFFFAOYSA-N [PH4+].I(=O)(=O)[O-] Chemical compound [PH4+].I(=O)(=O)[O-] RRLCRPBPKLRKMD-UHFFFAOYSA-N 0.000 description 4
- 230000031709 bromination Effects 0.000 description 4
- 238000005893 bromination reaction Methods 0.000 description 4
- 150000004694 iodide salts Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 150000001649 bromium compounds Chemical class 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 241000555268 Dendroides Species 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 150000004699 copper complex Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005166 mechanoluminescence Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 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 1
- SDFLTYHTFPTIGX-UHFFFAOYSA-N C[n]1c2ccccc2c2ccccc12 Chemical compound C[n]1c2ccccc2c2ccccc12 SDFLTYHTFPTIGX-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- RFDGVZHLJCKEPT-UHFFFAOYSA-N tris(2,4,6-trimethyl-3-pyridin-3-ylphenyl)borane Chemical compound CC1=C(B(C=2C(=C(C=3C=NC=CC=3)C(C)=CC=2C)C)C=2C(=C(C=3C=NC=CC=3)C(C)=CC=2C)C)C(C)=CC(C)=C1C1=CC=CN=C1 RFDGVZHLJCKEPT-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
- C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
- C07F9/655354—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring condensed with carbocyclic rings or carbocyclic ring systems
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
- C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero atom
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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Abstract
A kind of double phosphine copper cluster electroluminescent materials of feature based on dibenzothiophenes group and preparation method and application, it is related to a kind of electroluminescent material and preparation method and application.The invention aims to solve, existing cluster compound electroluminescent material photobleaching is strong, carrier transport ability is weak, stability of photoluminescence is poor, self-absorption is strong and the shortcoming of mulecular luminescence quenching.A kind of structural formula of the double phosphine copper cluster electroluminescent materials of feature based on dibenzothiophenes group is：Method：Feature biphosphine ligand, cuprous halide and dichloromethane are mixed, reaction, then be spin-dried for, obtain solid matter；Purified for eluent carries out column chromatography using the mixed liquor of dichloromethane and petroleum ether, that is, completed.A kind of double phosphine copper cluster electroluminescent materials of feature based on dibenzothiophenes group are applied as emitting layer material in electroluminescent device.The present invention can obtain a kind of double phosphine copper cluster electroluminescent materials of feature based on dibenzothiophenes group.
Description
Technical field
The present invention relates to a kind of electroluminescent material and preparation method and application.
Background technology
Organic electroluminescent LED shows and lighting engineering have at aspects such as energy-conserving and environment-protective referred to as third generation plane
Prominent advantage.The complex that metal is formed with organic molecule is due to its unique orbit coupling mode so that complex has
Phosphorescent or fluorescence characteristic, but due to heavy metals, these metal storages such as traditional complex material big multiplex gold, platinum
Scarcity, exploitation is difficult, involves great expense, thus it is desirable to it is more cheap, be more easy to obtain and nontoxic metal replaces valuable
Metal, and copper complex, environment-friendly because its is with low cost, lighting has the characteristics such as hot activation delayed fluorescence, progressively turns into
The favorable substitutes of precious metal complex.
In copper complex, cluster compound is still present many performance deficiencies, and such as carrier transport ability is weak, luminous intensity is low,
Molecule self-absorption is serious, luminescence queenching the problems such as.Additionally, the shortcomings of dissolubility of cluster compound is poor, Cluster Structures are easily broken, increases
The difficulty of its reprocessing.For example, the compound dissolubility synthesized by Braga seminars is poor, and during evaporation, molecule
Cluster Structures are broken, and cause device to be deposited with failure.It is therefore desirable to obtain a kind of cluster compound with premium properties：It is stronger
Carrier transport ability, luminous intensity high, preferable dissolubility, stabilization and controllable luminous, big Stokes shift,
Easy to process the features such as.
The content of the invention
The invention aims to solve, existing cluster compound electroluminescent material photobleaching is strong, carrier transport ability
Weak, stability of photoluminescence is poor, self-absorption is strong and the shortcoming of mulecular luminescence quenching, and provides a kind of based on dibenzothiophenes group
The double phosphine copper cluster electroluminescent materials of feature and preparation method and application.
A kind of structural formula of the double phosphine copper cluster electroluminescent materials of feature based on dibenzothiophenes group is：Wherein, described X is Cl, Br or I；Described Z be H, Described PPh2Structure be
Principle of the invention and advantage：
First, the double phosphine copper cluster electroluminescent materials of the feature based on dibenzothiophenes group prepared by the present invention can use
In preparing electroluminescent device；Whole molecule has big Stokes shift, fluorescence intensity high, adjustable fluorescent emission
With stability of photoluminescence high, the advantages of stronger carrier transport, the performance with luminescence generated by light, mechanoluminescence also has concurrently
The characteristics of electroluminescent；It is effective to solve that the Bleachability strong, carrier transport ability of copper luminescent material light is weak, stability of photoluminescence
Difference, the shortcomings of luminous uncontrollable, self-absorption is strong, molecule is quenched；
2nd, the double phosphine copper cluster electroluminescent materials of the feature based on dibenzothiophenes group prepared by the present invention have
The luminous characteristics such as mechanoluminescence, luminescence generated by light, electroluminescent, the function based on dibenzothiophenes group of being prepared using the present invention
Property the luminescent device for preparing of double phosphine copper cluster electroluminescent materials, its current efficiency maximum is 21.5cdA-1, outer quantum
Maximum efficiency is 9.8%, and power efficiency maximum is 27.7lm/W；
3rd, the double phosphine copper cluster electroluminescent materials of the feature based on dibenzothiophenes group prepared by the present invention have
Preferable stability of photoluminescence, is not likely to produce photobleaching；
4th, the double phosphine copper cluster electroluminescent materials of the feature based on dibenzothiophenes group prepared by the present invention light
210nm is reached with larger Stokes shift；
5th, the double phosphine copper cluster electroluminescent material current-carrying of the feature based on dibenzothiophenes group prepared by the present invention
Sub- transmittability is stronger；
6th, present invention uses the double phosphine groups of feature as part, with more excellent luminescent properties；
7th, the double phosphine copper cluster electroluminescent materials of the feature based on dibenzothiophenes group prepared using the present invention
The external quantum efficiency of the luminescent device of preparation up to 20.0%, with good thermodynamic stability, cracking temperature is 290 DEG C~
320 DEG C, while luminous efficiency and the brightness of electroluminescent organic material are improve, present invention is mainly applied to organic electroluminescent
In diode component.The present invention can obtain a kind of double phosphine copper cluster electroluminescence materials of feature based on dibenzothiophenes group
Material.
Brief description of the drawings
Fig. 1 is the double phosphine electroluminescent hairs of stannous chloride cluster compound of the feature based on dibenzothiophenes group prepared by embodiment one
Luminescent material is dissolved in the curve of spectrum in dichloromethane, and " ■ " is ultra-violet absorption spectrum curve in Fig. 1, and " " is fluorescence emission spectrum
Curve；
Fig. 2 is the double phosphine electroluminescent hairs of cuprous bromide cluster compound of the feature based on dibenzothiophenes group prepared by embodiment two
Luminescent material is dissolved in the curve of spectrum in dichloromethane, and " ■ " is ultra-violet absorption spectrum curve in Fig. 2, and " " is fluorescence emission spectrum
Curve；
Fig. 3 is the double phosphine electroluminescent hairs of cuprous iodide cluster compound of the feature based on dibenzothiophenes group prepared by embodiment three
Luminescent material is dissolved in the curve of spectrum in dichloromethane, and " ■ " is ultra-violet absorption spectrum curve in Fig. 3, and " " is fluorescence emission spectrum
Curve；
Fig. 4 is the double phosphine stannous chloride cluster compound electricity of the feature based on dibenzothiophenes group prepared using embodiment one
The efficiency chart of electroluminescent device prepared by electroluminescent material, 1 is current efficiency-brightness curve in Fig. 4, and 2 is power efficiency-bright
Write music line, 3 is external quantum efficiency-brightness curve；
Fig. 5 is the double phosphine cuprous bromide cluster compound electricity of the feature based on dibenzothiophenes group prepared using embodiment two
The efficiency chart of electroluminescent device prepared by electroluminescent material, 1 is current efficiency-brightness curve in Fig. 5, and 2 is power efficiency-bright
Write music line, 3 is external quantum efficiency-brightness curve；
Fig. 6 is the double phosphine cuprous iodide cluster compound electricity of the feature based on dibenzothiophenes group prepared using embodiment three
The efficiency chart of electroluminescent device prepared by electroluminescent material, 1 is current efficiency-brightness curve in Fig. 6, and 2 is power efficiency-bright
Write music line, 3 is external quantum efficiency-brightness curve；
Fig. 7 is the double phosphine stannous chlorides of the feature based on bis- carbazoles of 4,7--dibenzothiophenes group prepared by example IV
Cluster compound electroluminescent material is dissolved in the curve of spectrum in dichloromethane, and " ■ " is ultra-violet absorption spectrum curve in Fig. 7, and " " is
Fluorescence emission spectral curve；
Fig. 8 is the double phosphine cuprous bromides of the feature based on bis- carbazoles of 4,7--dibenzothiophenes group prepared by embodiment five
Cluster compound electroluminescent material is dissolved in the curve of spectrum in dichloromethane, and " ■ " is ultra-violet absorption spectrum curve in Fig. 8, and " " is
Fluorescence emission spectral curve；
Fig. 9 is the double phosphine cuprous iodides of the feature based on bis- carbazoles of 4,7--dibenzothiophenes group prepared by embodiment six
Cluster compound electroluminescent material is dissolved in the curve of spectrum in dichloromethane, and " ■ " is ultra-violet absorption spectrum curve in Fig. 9, and " " is
Fluorescence emission spectral curve；
Figure 10 is using the double phosphine protochlorides of the features based on bis- carbazoles of 4,7--dibenzothiophenes group for implementing four preparations
The efficiency chart of electroluminescent device prepared by copper cluster electroluminescent material, 1 is current efficiency-brightness curve in Figure 10, and 2 are
Power efficiency-brightness curve, 3 is external quantum efficiency-brightness curve；
Figure 11 is using the double phosphine protobromides of the features based on bis- carbazoles of 4,7--dibenzothiophenes group for implementing five preparations
The efficiency chart of electroluminescent device prepared by copper cluster electroluminescent material, 1 is current efficiency-brightness curve in Figure 11, and 2 are
Power efficiency-brightness curve, 3 is external quantum efficiency-brightness curve；
Figure 12 is sub- using the double phosphines iodate of six features based on bis- carbazoles of 4,7--dibenzothiophenes group for preparing is implemented
The efficiency chart of electroluminescent device prepared by copper cluster electroluminescent material, 1 is current efficiency-brightness curve in Figure 12, and 2 are
Power efficiency-brightness curve, 3 is external quantum efficiency-brightness curve；
Figure 13 is the double phosphine chlorine of the feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group prepared by embodiment seven
Change the curve of spectrum that cuprous cluster compound electroluminescent material is dissolved in dichloromethane, " ■ " is bent ultra-violet absorption spectrum in Figure 13
Line, " " is fluorescence emission spectral curve；
Figure 14 is the double phosphine bromines of the feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group prepared by embodiment eight
Change the curve of spectrum that cuprous cluster compound electroluminescent material is dissolved in dichloromethane, " ■ " is bent ultra-violet absorption spectrum in Figure 14
Line, " " is fluorescence emission spectral curve；
Figure 15 is the double phosphine iodine of the feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group prepared by embodiment nine
Change the curve of spectrum that cuprous cluster compound electroluminescent material is dissolved in dichloromethane, " ■ " is bent ultra-violet absorption spectrum in Figure 15
Line, " " is fluorescence emission spectral curve；
Figure 16 is using the double phosphine chlorine of the features based on 4,7- di-t-butyls carbazole-dibenzothiophenes group for implementing seven preparations
Change the efficiency chart of electroluminescent device prepared by cuprous cluster compound electroluminescent material, 1 is bent current efficiency-brightness in Figure 16
Line, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 17 is the feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group pair prepared using embodiment eight
The efficiency chart of electroluminescent device prepared by phosphine cuprous bromide cluster compound electroluminescent material, 1 is current efficiency-brightness in Figure 17
Curve, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 18 is the feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group pair prepared using embodiment nine
The efficiency chart of electroluminescent device prepared by phosphine cuprous iodide cluster compound electroluminescent material, 1 is current efficiency-brightness in Figure 18
Curve, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 19 is the double phosphine stannous chlorides of the feature based on 4,7- diphenylamines-dibenzothiophenes group prepared by embodiment ten
Cluster compound electroluminescent material is dissolved in the curve of spectrum in dichloromethane, and " ■ " is ultra-violet absorption spectrum curve, " " in Figure 19
It is fluorescence emission spectral curve；
Figure 20 is the double phosphine protobromides of the feature based on 4,7- diphenylamines-dibenzothiophenes group prepared by embodiment 11
Copper cluster electroluminescent material is dissolved in the curve of spectrum in dichloromethane, and " ■ " is ultra-violet absorption spectrum curve in Figure 20,
" " is fluorescence emission spectral curve；
Figure 21 is that the double phosphines iodate of the feature based on 4,7- diphenylamines-dibenzothiophenes group prepared by embodiment 12 is sub-
Copper cluster electroluminescent material is dissolved in the curve of spectrum in dichloromethane, and " ■ " is ultra-violet absorption spectrum curve in Figure 21,
" " is fluorescence emission spectral curve；
Figure 22 is the double phosphine chlorinations of the feature based on 4,7- diphenylamines-dibenzothiophenes group prepared using embodiment ten
The efficiency chart of electroluminescent device prepared by cuprous cluster compound electroluminescent material, 1 is current efficiency-brightness curve, 2 in Figure 22
It is power efficiency-brightness curve, 3 is external quantum efficiency-brightness curve；
Figure 23 is the double phosphine bromines of the feature based on 4,7- diphenylamines-dibenzothiophenes group prepared using embodiment 11
Change the efficiency chart of electroluminescent device prepared by cuprous cluster compound electroluminescent material, 1 is bent current efficiency-brightness in Figure 23
Line, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 24 is the double phosphine iodine of the feature based on 4,7- diphenylamines-dibenzothiophenes group prepared using embodiment 12
Change the efficiency chart of electroluminescent device prepared by cuprous cluster compound electroluminescent material, 1 is bent current efficiency-brightness in Figure 24
Line, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 25 is the double phosphine protochlorides of the feature based on 4,7- triphenylamines-dibenzothiophenes group prepared by embodiment 13
Copper cluster electroluminescent material is dissolved in the curve of spectrum in dichloromethane, and " ■ " is ultra-violet absorption spectrum curve in Figure 25,
" " is fluorescence emission spectral curve；
Figure 26 is the double phosphine protobromides of the feature based on 4,7- triphenylamines-dibenzothiophenes group prepared by embodiment 14
Copper cluster electroluminescent material is dissolved in the curve of spectrum in dichloromethane, and " ■ " is ultra-violet absorption spectrum curve in Figure 26,
" " is fluorescence emission spectral curve；
Figure 27 is that the double phosphines iodate of the feature based on 4,7- triphenylamines-dibenzothiophenes group prepared by embodiment 15 is sub-
Copper cluster electroluminescent material is dissolved in the curve of spectrum in dichloromethane, and " ■ " is ultra-violet absorption spectrum curve in Figure 27,
" " is fluorescence emission spectral curve；
Figure 28 is the double phosphine chlorine of the feature based on 4,7- triphenylamines-dibenzothiophenes group prepared using embodiment 13
Change the efficiency chart of electroluminescent device prepared by cuprous cluster compound electroluminescent material, 1 is bent current efficiency-brightness in Figure 28
Line, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 29 is the double phosphine bromines of the feature based on 4,7- triphenylamines-dibenzothiophenes group prepared using embodiment 14
Change the efficiency chart of electroluminescent device prepared by cuprous cluster compound electroluminescent material, 1 is bent current efficiency-brightness in Figure 29
Line, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 30 is the double phosphine iodine of the feature based on 4,7- triphenylamines-dibenzothiophenes group prepared using embodiment 15
Change the efficiency chart of electroluminescent device prepared by cuprous cluster compound electroluminescent material, 1 is bent current efficiency-brightness in Figure 30
Line, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 31 is the double phosphine chlorine of the feature based on 4,7- dendroids carbazole-dibenzothiophenes group prepared by embodiment 16
Change the curve of spectrum that cuprous cluster compound electroluminescent material is dissolved in dichloromethane, " ■ " is bent ultra-violet absorption spectrum in Figure 31
Line, " " is fluorescence emission spectral curve；
Figure 32 is the double phosphine bromines of the feature based on 4,7- dendroids carbazole-dibenzothiophenes group prepared by embodiment 17
Change the curve of spectrum that cuprous cluster compound electroluminescent material is dissolved in dichloromethane, " ■ " is bent ultra-violet absorption spectrum in Figure 32
Line, " " is fluorescence emission spectral curve；
Figure 33 is the double phosphine iodine of the feature based on 4,7- dendroids carbazole-dibenzothiophenes group prepared by embodiment 18
Change the curve of spectrum that cuprous cluster compound electroluminescent material is dissolved in dichloromethane, " ■ " is bent ultra-violet absorption spectrum in Figure 33
Line, " " is fluorescence emission spectral curve；
Figure 34 is the feature based on 4,7- dendroids carbazole-dibenzothiophenes group pair prepared using embodiment 16
The efficiency chart of electroluminescent device prepared by phosphine stannous chloride cluster compound electroluminescent material, 1 is current efficiency-brightness in Figure 34
Curve, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 35 is the feature based on 4,7- dendroids carbazole-dibenzothiophenes group pair prepared using embodiment 17
The efficiency chart of electroluminescent device prepared by phosphine cuprous bromide cluster compound electroluminescent material, 1 is current efficiency-brightness in Figure 35
Curve, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 36 is the feature based on 4,7- dendroids carbazole-dibenzothiophenes group pair prepared using embodiment 18
The efficiency chart of electroluminescent device prepared by phosphine cuprous iodide cluster compound electroluminescent material, 1 is current efficiency-brightness in Figure 36
Curve, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 37 is the feature based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group prepared by embodiment 19
Double phosphine stannous chloride cluster compound electroluminescent materials are dissolved in the curve of spectrum in dichloromethane, and " ■ " is UV absorption light in Figure 37
Spectral curve, " " is fluorescence emission spectral curve；
Figure 38 is the feature based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group prepared by embodiment 20
Double phosphine cuprous bromide cluster compound electroluminescent materials are dissolved in the curve of spectrum in dichloromethane, and " ■ " is UV absorption light in Figure 38
Spectral curve, " " is fluorescence emission spectral curve；
Figure 39 is the function based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group prepared by embodiment 21
Property double phosphine cuprous iodide cluster compound electroluminescent materials be dissolved in the curve of spectrum in dichloromethane, " ■ " is UV absorption in Figure 39
The curve of spectrum, " " is fluorescence emission spectral curve；
Figure 40 is the work(based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group prepared using embodiment 19
The efficiency chart of electroluminescent device prepared by the double phosphine stannous chloride cluster compound electroluminescent materials of energy property, 1 is that electric current is imitated in Figure 40
Rate-brightness curve, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 41 is the work(based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group prepared using embodiment 20
The efficiency chart of electroluminescent device prepared by the double phosphine cuprous bromide cluster compound electroluminescent materials of energy property, 1 is that electric current is imitated in Figure 41
Rate-brightness curve, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 42 is based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group using the preparation of embodiment 21
The efficiency chart of electroluminescent device prepared by the double phosphine cuprous iodide cluster compound electroluminescent materials of feature, 1 is electric current in Figure 42
Ciency-luminance curve, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 43 is the function based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group prepared by embodiment 22
Property double phosphine stannous chloride cluster compound electroluminescent materials be dissolved in the curve of spectrum in dichloromethane, " ■ " is UV absorption in Figure 43
The curve of spectrum, " " is fluorescence emission spectral curve；
Figure 44 is the function based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group prepared by embodiment 23
Property double phosphine cuprous bromide cluster compound electroluminescent materials be dissolved in the curve of spectrum in dichloromethane, " ■ " is UV absorption in Figure 44
The curve of spectrum, " " is fluorescence emission spectral curve；
Figure 45 is the function based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group prepared by embodiment 24
Property double phosphine cuprous iodide cluster compound electroluminescent materials be dissolved in the curve of spectrum in dichloromethane, " ■ " is UV absorption in Figure 45
The curve of spectrum, " " is fluorescence emission spectral curve；
Figure 46 is based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group using the preparation of embodiment 22
The efficiency chart of electroluminescent device prepared by the double phosphine stannous chloride cluster compound electroluminescent materials of feature, 1 is electric current in Figure 46
Ciency-luminance curve, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 47 is based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group using the preparation of embodiment 23
The efficiency chart of electroluminescent device prepared by the double phosphine cuprous bromide cluster compound electroluminescent materials of feature, 1 is electric current in Figure 47
Ciency-luminance curve, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 48 is based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group using the preparation of embodiment 24
The efficiency chart of electroluminescent device prepared by the double phosphine cuprous iodide cluster compound electroluminescent materials of feature, 1 is electric current in Figure 48
Ciency-luminance curve, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 49 is the function based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group prepared by embodiment 25
Property double phosphine stannous chloride cluster compound electroluminescent materials be dissolved in the curve of spectrum in dichloromethane, " ■ " is UV absorption in Figure 49
The curve of spectrum, " " is fluorescence emission spectral curve；
Figure 50 is the function based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group prepared by embodiment 26
Property double phosphine cuprous bromide cluster compound electroluminescent materials be dissolved in the curve of spectrum in dichloromethane, " ■ " is UV absorption in Figure 50
The curve of spectrum, " " is fluorescence emission spectral curve；
Figure 51 is the function based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group prepared by embodiment 27
Property double phosphine cuprous iodide cluster compound electroluminescent materials be dissolved in the curve of spectrum in dichloromethane, " ■ " is UV absorption in Figure 51
The curve of spectrum, " " is fluorescence emission spectral curve；
Figure 52 is based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group using the preparation of embodiment 25
The efficiency chart of electroluminescent device prepared by the double phosphine stannous chloride cluster compound electroluminescent materials of feature, 1 is electric current in Figure 52
Ciency-luminance curve, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 53 is based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group using the preparation of embodiment 26
The efficiency chart of electroluminescent device prepared by the double phosphine cuprous bromide cluster compound electroluminescent materials of feature, 1 is electric current in Figure 53
Ciency-luminance curve, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 54 is based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group using the preparation of embodiment 27
The efficiency chart of electroluminescent device prepared by the double phosphine cuprous iodide cluster compound electroluminescent materials of feature, 1 is electric current in Figure 54
Ciency-luminance curve, 2 is power efficiency-brightness curve, and 3 is external quantum efficiency-brightness curve；
Figure 55 is the double phosphine stannous chloride cluster compounds of the feature based on dibenzothiophenes group prepared using embodiment one
EL spectra figure prepared by electroluminescent material；
Figure 56 is the double phosphine cuprous bromide cluster compounds of the feature based on dibenzothiophenes group prepared using embodiment two
EL spectra figure prepared by electroluminescent material；
Figure 57 is the double phosphine cuprous iodide cluster compounds of the feature based on dibenzothiophenes group prepared using embodiment three
EL spectra figure prepared by electroluminescent material；
Figure 58 is the double phosphine chlorinations of the feature based on bis- carbazoles of 4,7--dibenzothiophenes group prepared using example IV
EL spectra figure prepared by cuprous cluster compound electroluminescent material；
Figure 59 is the double phosphine bromine chlorine of the feature based on bis- carbazoles of 4,7--dibenzothiophenes group prepared using embodiment five
Change EL spectra figure prepared by cuprous cluster compound electroluminescent material；
Figure 60 is the double phosphine iodate of the feature based on bis- carbazoles of 4,7--dibenzothiophenes group prepared using embodiment six
EL spectra figure prepared by cuprous cluster compound electroluminescent material；
Figure 61 is the feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group pair prepared using embodiment seven
EL spectra figure prepared by phosphine stannous chloride cluster compound electroluminescent material；
Figure 62 is the feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group pair prepared using embodiment eight
EL spectra figure prepared by phosphine cuprous bromide cluster compound electroluminescent material；
Figure 63 is the feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group pair prepared using embodiment nine
EL spectra figure prepared by phosphine cuprous iodide cluster compound electroluminescent material；
Figure 64 is the double phosphine chlorinations of the feature based on 4,7- diphenylamines-dibenzothiophenes group prepared using embodiment ten
EL spectra figure prepared by cuprous cluster compound electroluminescent material；
Figure 65 is the double phosphine bromines of the feature based on 4,7- diphenylamines-dibenzothiophenes group prepared using embodiment 11
Change EL spectra figure prepared by cuprous cluster compound electroluminescent material；
Figure 66 is the double phosphine iodine of the feature based on 4,7- diphenylamines-dibenzothiophenes group prepared using embodiment 12
Change EL spectra figure prepared by cuprous cluster compound electroluminescent material；
Figure 67 is the double phosphine chlorine of the feature based on 4,7- triphenylamines-dibenzothiophenes group prepared using embodiment 13
Change EL spectra figure prepared by cuprous cluster compound electroluminescent material；
Figure 68 is the double phosphine bromines of the feature based on 4,7- triphenylamines-dibenzothiophenes group prepared using embodiment 14
Change EL spectra figure prepared by cuprous cluster compound electroluminescent material；
Figure 69 is the double phosphine iodine of the feature based on 4,7- triphenylamines-dibenzothiophenes group prepared using embodiment 15
Change EL spectra figure prepared by cuprous cluster compound electroluminescent material；
Figure 70 is the feature based on 4,7- dendroids carbazole-dibenzothiophenes group pair prepared using embodiment 16
EL spectra figure prepared by phosphine stannous chloride cluster compound electroluminescent material；
Figure 71 is the feature based on 4,7- dendroids carbazole-dibenzothiophenes group pair prepared using embodiment 17
EL spectra figure prepared by phosphine cuprous bromide cluster compound electroluminescent material；
Figure 72 is the feature based on 4,7- dendroids carbazole-dibenzothiophenes group pair prepared using embodiment 18
EL spectra figure prepared by phosphine cuprous iodide cluster compound electroluminescent material；
Figure 73 is the work(based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group prepared using embodiment 19
EL spectra figure prepared by the double phosphine stannous chloride cluster compound electroluminescent materials of energy property；
Figure 74 is the work(based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group prepared using embodiment 20
EL spectra figure prepared by the double phosphine cuprous bromide cluster compound electroluminescent materials of energy property；
Figure 75 is based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group using the preparation of embodiment 21
EL spectra figure prepared by the double phosphine cuprous iodide cluster compound electroluminescent materials of feature；
Figure 76 is based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group using the preparation of embodiment 22
EL spectra figure prepared by the double phosphine stannous chloride cluster compound electroluminescent materials of feature；
Figure 77 is based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group using the preparation of embodiment 23
EL spectra figure prepared by the double phosphine cuprous bromide cluster compound electroluminescent materials of feature；
Figure 78 is based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group using the preparation of embodiment 24
EL spectra figure prepared by the double phosphine cuprous iodide cluster compound electroluminescent materials of feature；
Figure 79 is based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group using the preparation of embodiment 25
EL spectra figure prepared by the double phosphine stannous chloride cluster compound electroluminescent materials of feature；
Figure 80 is based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group using the preparation of embodiment 26
EL spectra figure prepared by the double phosphine cuprous bromide cluster compound electroluminescent materials of feature；
Figure 81 is based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group using the preparation of embodiment 27
EL spectra figure prepared by the double phosphine cuprous bromide cluster compound electroluminescent materials of feature.
Specific embodiment
Specific embodiment one：Present embodiment is a kind of double phosphine copper clusters of feature based on dibenzothiophenes group
What the preparation method of electroluminescent material was specifically realized by the following steps：
Feature biphosphine ligand, cuprous halide and dichloromethane are mixed, then 10h is reacted in the case where temperature is for 40 DEG C~45 DEG C
~15h, reuses Rotary Evaporators and is spin-dried for, and obtains solid matter；The use of the mixed liquor of dichloromethane and petroleum ether is eluent
Column chromatography purifying is carried out, the double phosphine copper cluster electroluminescent materials of the feature based on dibenzothiophenes group are obtained；
Described feature biphosphine ligand is (0.5~3) with the amount ratio of the material of cuprous halide:1；Described feature is double
The amount of the material of Phosphine ligands is 1mmol with the volume ratio of dichloromethane:(3mL~10mL)；Described feature biphosphine ligand isWherein, described Z be H, Described PPh2Structure be
Specific embodiment two：Present embodiment is with the difference of specific embodiment one：Described dichloromethane and
Dichloromethane and the volume ratio of petroleum ether are 1 in the mixed liquor of petroleum ether:20.Other are identical with specific embodiment one.
Specific embodiment three：Present embodiment is with the difference of specific embodiment one or two：Described feature
Biphosphine ligand is (1~3) with the amount ratio of the material of cuprous halide:1.Other are identical with one of specific embodiment one or two.
Specific embodiment four：Present embodiment is with the difference of specific embodiment one to three：Described feature
Biphosphine ligand is (2~3) with the amount ratio of the material of cuprous halide:1.Other are identical with one of specific embodiment one to three.
Specific embodiment five：Present embodiment is with the difference of specific embodiment one to four：Described feature
The amount of the material of biphosphine ligand is 1mmol with the volume ratio of dichloromethane:(3mL~5mL).Other with specific embodiment one to
One of four is identical.
Specific embodiment six：Present embodiment is with the difference of specific embodiment one to five：Described feature
The amount of the material of biphosphine ligand is 1mmol with the volume ratio of dichloromethane:(5mL~10mL).Other and specific embodiment one
It is identical to one of five.
Specific embodiment seven：Present embodiment is with the difference of specific embodiment one to six：Described halogenation is sub-
Copper is stannous chloride, cuprous bromide or cuprous iodide.Other are identical with one of specific embodiment one to six.
Specific embodiment eight：Present embodiment is with the difference of specific embodiment one to seven：By the double phosphines of feature
The mixing of part, cuprous halide and dichloromethane, then 10h~13h is reacted in the case where temperature is for 40 DEG C~45 DEG C, reuse rotary evaporation
Instrument is spin-dried for, and obtains solid matter；Using the mixed liquor of dichloromethane and petroleum ether for eluent carries out column chromatography purifying, base is obtained
In the double phosphine copper cluster electroluminescent materials of the feature of dibenzothiophenes group.Other are one of with specific embodiment one to seven
It is identical.
Specific embodiment nine：Present embodiment is a kind of double phosphine copper clusters of feature based on dibenzothiophenes group
Electroluminescent material is applied as emitting layer material in electroluminescent device.
Embodiment one to embodiment 27 is illustrated with reference to Fig. 1~Figure 81.
Embodiment one：A kind of double phosphine stannous chloride cluster compound electroluminescent materials of feature based on dibenzothiophenes group
Preparation method be specifically realized by the following steps：
1mmol features biphosphine ligand, 1mmol cuprous halides and 5mL dichloromethane are mixed, then in the case where temperature is for 45 DEG C
Reaction 13h, reuses Rotary Evaporators and is spin-dried for, and obtains solid matter；The use of the mixed liquor of dichloromethane and petroleum ether is drip washing
Agent carries out column chromatography purifying, obtains the double phosphine stannous chloride cluster compound electroluminescence materials of the feature based on dibenzothiophenes group
Material；
Described feature biphosphine ligand isWherein, described Z is H；Described cuprous halide is chlorination
It is cuprous；Dichloromethane and the volume ratio of petroleum ether are 1 in described dichloromethane and the mixed liquor of petroleum ether:20.
The double phosphine stannous chloride cluster compound electroluminescence materials of feature based on dibenzothiophenes group prepared by embodiment one
The structural formula of material is：Wherein, described X is Cl；Described Z is H；
The double phosphine stannous chloride clusters of the feature based on dibenzothiophenes group prepared using Mass Spectrometer Method embodiment one are closed
Thing electroluminescent material, testing result is as follows：Exace mass:1495.84；m/z:1499.84 (100.0%)；Elemental
Analysis for C72H52Cl4Cu4P4S2：C,57.61；H,3.49；S,4.27.
The application test of embodiment one：The double phosphine chlorine of the feature based on dibenzothiophenes group prepared using embodiment one
The method for changing electroluminescent device prepared by cuprous cluster compound electroluminescent material is as follows：
First, the glass cleaned through deionized water is put into vacuum evaporation instrument, vacuum is 1 × 10-6Mbar, evaporation rate sets
It is 0.2nm s-1, deposition material is tin indium oxide (ITO) on glass, and thickness is the anode conductive layer of 100nm；
2nd, hole transport layer material TAPC is deposited with hole injection layer, thickness is obtained for 30nm hole transmission layers；
3rd, barrier material mCP is deposited with hole transmission layer, thickness is obtained for 10nm exciton barrier-layers；
4th, the double phosphine chlorinations of the feature based on dibenzothiophenes group prepared by embodiment one are deposited with exciton barrier-layer
Cuprous cluster compound electroluminescent material, obtains thickness for 25nm luminescent layers；
5th, electron transport layer materials 3TPYMB is deposited with hole blocking layer, thickness is 50nm electron transfer layers；
6th, electron injecting layer material LiF is deposited with the electron transport layer, and thickness is 0.5nm electron injecting layers；
7th, deposition material is metal on electron injecting layer, and thickness is the cathode conductive layer of 100nm, is utilized implementation
Prepared by the double phosphine stannous chloride cluster compound electroluminescent materials of the feature based on dibenzothiophenes group prepared by example one electroluminescent
Luminescent device；
Metal described in step 7 is aluminium.
From fig. 1, it can be seen that the double phosphine stannous chloride cluster compounds of the feature based on dibenzothiophenes group prepared by embodiment one
UV absorption is 282nm, and fluorescent emission is 520nm.As can be seen from Figure 4, using the preparation of embodiment one based on dibenzothiophenes base
The maximum external quantum efficiency of electroluminescent device prepared by the double phosphine stannous chloride cluster compound electroluminescent materials of feature of group is
9.8%, maximum current efficiency is 20.0cdA-1, power efficiency is 24.1lm/W.
Embodiment two：It is electroluminescent that the present embodiment prepares the double phosphine cuprous bromide cluster compounds of the feature based on dibenzothiophenes group
The method of luminescent material is with the difference of embodiment one：Described feature biphosphine ligand isWherein, it is described
Z be H；Described cuprous halide is cuprous bromide.Other are identical with embodiment one.
The double phosphine cuprous bromide cluster compound electroluminescence materials of feature based on dibenzothiophenes group prepared by embodiment two
The structural formula of material is：Wherein, described X is Br；Described Z is H.
The double phosphine cuprous bromide clusters of the feature based on dibenzothiophenes group prepared using Mass Spectrometer Method embodiment two are closed
Thing electroluminescent material, testing result is as follows：Exace mass:1671.64；m/z:1677.63 (100.0%)；Elemental
Analysis for C72H52Br4Cu4P4S2:C,51.51；H,3.12；S,3.82.
The application test of embodiment two：This experiment is with the difference of the application test of embodiment one：Swashing in step 4
Emitting layer material embodiment two is deposited with sub- barrier layer and prepares the double phosphine cuprous bromide clusters of the feature based on dibenzothiophenes group
Compound electroluminescent material, obtains thickness for 25nm luminescent layers.Other application tests with embodiment one are identical.
As can be seen from Figure 2, the double phosphine cuprous bromide cluster compounds of the feature based on dibenzothiophenes group that prepared by embodiment two
UV absorption is 282nm, and fluorescent emission is 522nm.As can be seen from Figure 5, using the preparation of embodiment two based on dibenzothiophenes base
The maximum external quantum efficiency of electroluminescent device prepared by the double phosphine cuprous bromide cluster compound electroluminescent materials of feature of group is
6.5%, maximum current efficiency is 15.2cdA-1, power efficiency is 24.0lm/W.
Embodiment three：The double phosphine cuprous iodide cluster compound electricity of feature based on dibenzothiophenes group manufactured in the present embodiment
The method of electroluminescent material is with the difference of embodiment one：Described feature biphosphine ligand isWherein, it is described
Z be H；Described cuprous halide is cuprous iodide.Other are identical with embodiment one.
The double phosphine cuprous iodide cluster compound electroluminescence materials of feature based on dibenzothiophenes group prepared by embodiment three
The structural formula of material is：Wherein, described X is I；Described Z is H.
The double phosphine cuprous iodide clusters of the feature based on dibenzothiophenes group prepared using Mass Spectrometer Method embodiment three are closed
Thing electroluminescent material, testing result is as follows：Exace mass:Exace mass:1863.58；m/z:1865.58
(100.0%)；Elemental Analysis for C72H52I4Cu4P4S2:C,46.32；H,2.81；S,3.43.
The application test of embodiment three：This experiment is with the difference of the application test of embodiment one：Swashing in step 4
The double phosphine cuprous iodide cluster compounds of the feature based on dibenzothiophenes group that the preparation of embodiment three is deposited with sub- barrier layer are electroluminescent
Luminescent material, obtains thickness for 25nm luminescent layers.Other application tests with embodiment one are identical.
As can be seen from Figure 3, the double phosphine cuprous iodide cluster compounds of the feature based on dibenzothiophenes group that prepared by embodiment three
UV absorption is 282nm, and fluorescent emission is 522nm.As can be seen from Figure 6, using the preparation of embodiment three based on dibenzothiophenes base
The maximum external quantum efficiency of electroluminescent device prepared by the double phosphine cuprous iodide cluster compound electroluminescent materials of feature of group is
7.1%, maximum current efficiency is 15.8cdA-1, power efficiency is 22.1lm/W.
Example IV：The double phosphine chlorinations of feature based on bis- carbazoles of 4,7--dibenzothiophenes group manufactured in the present embodiment
The method of cuprous cluster compound electroluminescent material is with the difference of embodiment one：Described feature biphosphine ligand isWherein, described Z isDescribed cuprous halide is stannous chloride.Other with the phase of embodiment one
Together.
The double phosphine stannous chloride cluster compounds of feature based on bis- carbazoles of 4,7--dibenzothiophenes group prepared by example IV
The structural formula of electroluminescent material is：Wherein, described X is Cl；Described Z is
The double phosphine chlorine of the feature based on bis- carbazoles of 4,7--dibenzothiophenes group prepared using Mass Spectrometer Method example IV
Change cuprous cluster compound electroluminescent material, testing result is as follows：Exact Mass:2156.07；m/z:2161.07
(100.0%), Elemental Analysis for C120H80Cl4Cu4N4P4S2:C,66.67；H,3.73；S,2.97.
The application test of example IV：This experiment is with the difference of the application test of embodiment one：Swashing in step 4
The double phosphine stannous chlorides of the feature based on bis- carbazoles of 4,7--dibenzothiophenes group prepared by example IV are deposited with sub- barrier layer
Cluster compound electroluminescent material, obtains thickness for 25nm luminescent layers.Other application tests with embodiment one are identical.
As can be seen from Figure 7, the double phosphine chlorinations of the feature based on 4,7-, bis- carbazoles-dibenzothiophenes group that prepared by example IV
Cuprous cluster compound UV absorption is 282nm, and fluorescent emission is 520nm.As can be seen from Figure 10, using example IV preparation based on 4,
Electroluminescent cell prepared by the double phosphine stannous chloride cluster compound electroluminescent materials of the feature of bis- carbazoles of 7--dibenzothiophenes group
The maximum external quantum efficiency of part is 7.5%, and maximum current efficiency is 20.2cdA-1, power efficiency is 20.2lm/W.
Embodiment five：The double phosphine brominations of feature based on bis- carbazoles of 4,7--dibenzothiophenes group manufactured in the present embodiment
The method of cuprous cluster compound electroluminescent material is with the difference of embodiment one：Described feature biphosphine ligand isWherein, described Z isDescribed cuprous halide is cuprous bromide.Other with the phase of embodiment one
Together.
The double phosphine cuprous bromide cluster compounds of feature based on bis- carbazoles of 4,7--dibenzothiophenes group prepared by embodiment five
The structural formula of electroluminescent material is：Wherein, described X is Br；Described Z is
The double phosphine bromines of the feature based on bis- carbazoles of 4,7--dibenzothiophenes group prepared using Mass Spectrometer Method embodiment five
Change cuprous cluster compound electroluminescent material, testing result is as follows：Exact Mass:2331.87；m/z:2338.87
(100.0%), Elemental Analysis for C120H80Br4Cu4N4P4S2:C,61.60；H,3.45；S,2.74.
The application test of embodiment five：This experiment is with the difference of the application test of embodiment one：Swashing in step 4
The double phosphine chlorine protobromides of the feature based on bis- carbazoles of 4,7--dibenzothiophenes group prepared by embodiment five are deposited with sub- barrier layer
Copper cluster electroluminescent material, obtains thickness for 25nm luminescent layers.Other application tests with embodiment one are identical.
As it can be observed in the picture that the double phosphine brominations of the feature based on 4,7-, bis- carbazoles-dibenzothiophenes group prepared by embodiment five
Cuprous cluster compound UV absorption is 281nm, and fluorescent emission is 519nm.As can be seen from Figure 11, using the preparation of implementation five based on 4,7-
Electroluminescent device prepared by the double phosphine cuprous bromide cluster compound electroluminescent materials of the feature of two carbazoles-dibenzothiophenes group
Maximum external quantum efficiency be 8.1%, maximum current efficiency be 20.5cdA-1, power efficiency is 16.3lm/W.
Embodiment six：The double phosphine iodate of feature based on bis- carbazoles of 4,7--dibenzothiophenes group manufactured in the present embodiment
The method of cuprous cluster compound electroluminescent material is with the difference of embodiment one：Described feature biphosphine ligand isWherein, described Z isDescribed cuprous halide is cuprous iodide.Other with the phase of embodiment one
Together.
The double phosphine cuprous iodide cluster compounds of feature based on bis- carbazoles of 4,7--dibenzothiophenes group prepared by embodiment six
The structural formula of electroluminescent material is：Wherein, described X is I；Described Z is
The double phosphine iodine of the feature based on bis- carbazoles of 4,7--dibenzothiophenes group prepared using Mass Spectrometer Method embodiment six
Change cuprous cluster compound electroluminescent material, testing result is as follows：Exact Mass:2523.81；m/z:2526.82
(100.0%), Elemental Analysis for C120H80Cu4I4N4P4S2:C,57.02；H,3.19；S,2.54.
The application test of embodiment six：This experiment is with the difference of the application test of embodiment one：Swashing in step 4
The double phosphine cuprous iodides of the feature based on bis- carbazoles of 4,7--dibenzothiophenes group prepared by embodiment six are deposited with sub- barrier layer
Cluster compound electroluminescent material, obtains thickness for 25nm luminescent layers.Other application tests with embodiment one are identical.
As can be seen from Figure 9, embodiment six is based on the double phosphine cuprous iodide clusters of feature of 4,7-, bis- carbazoles-dibenzothiophenes group
Compound UV absorption is 281nm, and fluorescent emission is 521nm.As can be seen from Figure 12, using the preparation of embodiment six based on the clicks of 4,7- bis-
Electroluminescent device prepared by the double phosphine cuprous iodide cluster compound electroluminescent materials of the feature of azoles-dibenzothiophenes group is most
Big external quantum efficiency is 5.7%, and maximum current efficiency is 21.1cdA-1, power efficiency is 22.4lm/W.
Embodiment seven：Feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group manufactured in the present embodiment is double
The method of phosphine stannous chloride cluster compound electroluminescent material is with the difference of embodiment one：Described feature biphosphine ligand isWherein, described Z isDescribed cuprous halide is stannous chloride.Other with the phase of embodiment one
Together.
The double phosphine stannous chlorides of feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group prepared by embodiment seven
The structural formula of cluster compound electroluminescent material is：Wherein, described X is Cl；Described Z is
The feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group prepared using Mass Spectrometer Method embodiment seven
Double phosphine stannous chloride cluster compound electroluminescent materials, testing result is as follows：Exact Mass:2604.57；m/z:2609.57
(100.0%)；Elemental Analysis for C152H144Br4Cu4N4P4S:C,69.93；H,5.56；S,2.46.
The application test of embodiment seven：This experiment is with the difference of the application test of embodiment one：Swashing in step 4
The double phosphine chlorine of the feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group prepared by embodiment seven are deposited with sub- barrier layer
Change cuprous cluster compound electroluminescent material, obtain thickness for 25nm luminescent layers.Other application tests with embodiment one are identical.
As can be seen from Figure 13, the double phosphine stannous chloride clusters of the feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group
Compound UV absorption is 280nm, and fluorescent emission is 470nm.As can be seen from Figure 16, using the preparation of implementation seven based on the tertiary fourths of 4,7- bis-
Electroluminescent device prepared by the double phosphine stannous chloride cluster compound electroluminescent materials of the feature of base carbazole-dibenzothiophenes group
Maximum external quantum efficiency be 6.8%, maximum current efficiency be 13.1cdA-1, power efficiency is 18.7lm/W.
Embodiment eight：Feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group manufactured in the present embodiment is double
The method of phosphine cuprous bromide cluster compound electroluminescent material is with the difference of embodiment one：Described feature biphosphine ligand isWherein, described Z isDescribed cuprous halide is cuprous bromide.Other with the phase of embodiment one
Together.
The double phosphine cuprous bromides of feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group prepared by embodiment eight
The structural formula of cluster compound electroluminescent material is：Wherein, described X is Br；Described Z is
The feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group prepared using Mass Spectrometer Method embodiment eight
Double phosphine cuprous bromide cluster compound electroluminescent materials, testing result is as follows：Exact Mass:2780.37；m/z:2787.37
(100.0%)；Elemental Analysis for C152H144Br4Cu4N4P4S2:C,65.47；H,5.21；S,2.30.
The application test of embodiment eight：This experiment is with the difference of the application test of embodiment one：Swashing in step 4
The double phosphine bromines of the feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group prepared by embodiment eight are deposited with sub- barrier layer
Change cuprous cluster compound electroluminescent material, obtain thickness for 25nm luminescent layers.Other application tests with embodiment one are identical.
As can be seen from Figure 14, the double phosphine cuprous bromide clusters of the feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group
Compound UV absorption is 280nm, and fluorescent emission is 500nm.As can be seen from Figure 17, using the preparation of embodiment eight based on the uncles of 4,7- bis-
Electroluminescent cell prepared by the double phosphine cuprous bromide cluster compound electroluminescent materials of the feature of butyl carbazole-dibenzothiophenes group
The maximum external quantum efficiency of part is 8.0%, and maximum current efficiency is 20.8cdA-1, power efficiency is 21.7lm/W.
Embodiment nine：Feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group manufactured in the present embodiment is double
The method of phosphine cuprous iodide cluster compound electroluminescent material is with the difference of embodiment one：Described feature biphosphine ligand isWherein, described Z isDescribed cuprous halide is cuprous iodide.Other with the phase of embodiment one
Together.
The double phosphine cuprous iodides of feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group prepared by embodiment nine
The structural formula of cluster compound electroluminescent material is：Wherein, described X is I；Described Z is
The feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group prepared using Mass Spectrometer Method embodiment nine
Double phosphine cuprous iodide cluster compound electroluminescent materials, testing result is as follows：Exact Mass:2972.31；m/z:2975.32
(100.0%)；Elemental Analysis for C152H144Br4Cu4N4P4S2:C,61.33；H,4.88；S,2.15.
The application test of embodiment nine：This experiment is with the difference of the application test of embodiment one：Swashing in step 4
The double phosphine iodine of the feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group prepared by embodiment nine are deposited with sub- barrier layer
Change cuprous cluster compound electroluminescent material, obtain thickness for 25nm luminescent layers.Other application tests with embodiment one are identical.
From figure 15, it can be known that the feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group prepared by embodiment nine
Double phosphine cuprous iodide cluster compound UV absorptions are 280nm, and fluorescent emission is 490nm.As can be seen from Figure 18, prepared using embodiment nine
The double phosphine cuprous iodide cluster compound electroluminescent material systems of the feature based on 4,7- di-t-butyls carbazole-dibenzothiophenes group
The maximum external quantum efficiency of standby electroluminescent device is 6.5%, and maximum current efficiency is 21.4cdA-1, power efficiency is
25.0lm/W。
Embodiment ten：The double phosphine chlorinations of feature based on 4,7- diphenylamines-dibenzothiophenes group manufactured in the present embodiment
The method of cuprous cluster compound electroluminescent material is with the difference of embodiment one：Described feature biphosphine ligand isWherein, described Z isDescribed cuprous halide is stannous chloride.Other with embodiment one
It is identical.
The double phosphine stannous chloride cluster compounds of feature based on 4,7- diphenylamines-dibenzothiophenes group prepared by embodiment ten
The structural formula of electroluminescent material is：Wherein, described X is Cl；Described Z is
The double phosphine chlorine of the feature based on 4,7- diphenylamines-dibenzothiophenes group prepared using Mass Spectrometer Method embodiment ten
Change cuprous cluster compound electroluminescent material, testing result is as follows：Exact Mass:2164.13；m/z:2169.13
(100.0%)；Elemental Analysis for C120H88Cl4Cu4N4P4S2:C,66.42；H,4.09；S,2.95.
The application test of embodiment ten：This experiment is with the difference of the application test of embodiment one：Swashing in step 4
The double phosphine stannous chlorides of the feature based on 4,7- diphenylamines-dibenzothiophenes group prepared by embodiment ten are deposited with sub- barrier layer
Cluster compound electroluminescent material, obtains thickness for 25nm luminescent layers.Other application tests with embodiment one are identical.
As can be seen from Figure 19, the double phosphine chlorine of the feature based on 4,7- diphenylamines-dibenzothiophenes group that prepared by embodiment ten
Change cuprous cluster compound UV absorption for 280nm, fluorescent emission is 470nm.As can be seen from Figure 22, using embodiment ten prepare based on
Electroluminescent prepared by the double phosphine stannous chloride cluster compound electroluminescent materials of the feature of 4,7- diphenylamines-dibenzothiophenes group
The maximum external quantum efficiency of device is 7.5%, and maximum current efficiency is 18.0cdA-1, power efficiency is 19.6lm/W.
Embodiment 11：The double phosphine bromines of feature based on 4,7- diphenylamines-dibenzothiophenes group manufactured in the present embodiment
The method and the difference of embodiment one for changing cuprous cluster compound electroluminescent material be：Described feature biphosphine ligand isWherein, described Z isDescribed cuprous halide is cuprous bromide.Other are identical with embodiment one.
The double phosphine cuprous bromide clusters of feature based on 4,7- diphenylamines-dibenzothiophenes group prepared by embodiment 11 are closed
The structural formula of thing electroluminescent material is：Wherein, described X is Br；Described Z is
The double phosphines of the feature based on 4,7- diphenylamines-dibenzothiophenes group prepared using Mass Spectrometer Method embodiment 11
Cuprous bromide cluster compound electroluminescent material, testing result is as follows：Exact Mass:2339.93；m/z:2346.93
(100.0%)；Elemental Analysis for C120H88Br4Cu4N4P4S2:C,61.39；H,3.78；S,2.73.
The application test of embodiment 11：This experiment is with the difference of the application test of embodiment one：In step 4
The double phosphine brominations of the feature based on 4,7- diphenylamines-dibenzothiophenes group prepared by embodiment 11 are deposited with exciton barrier-layer
Cuprous cluster compound electroluminescent material, obtains thickness for 25nm luminescent layers.Other application tests with embodiment one are identical.
As can be seen from Figure 20, the double phosphines of the feature based on 4,7- diphenylamines-dibenzothiophenes group that prepared by embodiment 11
Cuprous bromide cluster compound UV absorption is 280nm, and fluorescent emission is 505nm.As can be seen from Figure 23, prepared using embodiment 11
Prepared by the double phosphine cuprous bromide cluster compound electroluminescent materials of the feature based on 4,7- diphenylamines-dibenzothiophenes group electroluminescent
The maximum external quantum efficiency of luminescent device is 6.8%, and maximum current efficiency is 19.8cdA-1, power efficiency is 20.0lm/W.
Embodiment 12：The double phosphine iodine of feature based on 4,7- diphenylamines-dibenzothiophenes group manufactured in the present embodiment
The method and the difference of embodiment one for changing cuprous cluster compound electroluminescent material be：Described feature biphosphine ligand isWherein, described Z isDescribed cuprous halide is cuprous iodide.Other with the phase of embodiment one
Together.
The double phosphine cuprous iodide clusters of feature based on 4,7- diphenylamines-dibenzothiophenes group prepared by embodiment 12 are closed
The structural formula of thing electroluminescent material is：Wherein, described X is I；Described Z is
The double phosphines of the feature based on 4,7- diphenylamines-dibenzothiophenes group prepared using Mass Spectrometer Method embodiment 12
Cuprous iodide cluster compound electroluminescent material, testing result is as follows：Exact Mass:2531.88；m/z:2534.88
(100.0%)；Elemental Analysis for C120H88I4Cu4N4P4S2:C,56.84；H,3.50；S,2.53.
The application test of embodiment 12：This experiment is with the difference of the application test of embodiment one：In step 4
The double phosphine iodate of the feature based on 4,7- diphenylamines-dibenzothiophenes group prepared by embodiment 12 are deposited with exciton barrier-layer
Cuprous cluster compound electroluminescent material, obtains thickness for 25nm luminescent layers.Other application tests with embodiment one are identical.
As can be seen from Figure 21, the double phosphines of the feature based on 4,7- diphenylamines-dibenzothiophenes group that prepared by embodiment 12
Cuprous iodide cluster compound UV absorption is 280nm, and fluorescent emission is 490nm.As can be seen from Figure 24, prepared using embodiment 12
Prepared by the double phosphine cuprous iodide cluster compound electroluminescent materials of the feature based on 4,7- diphenylamines-dibenzothiophenes group electroluminescent
The maximum external quantum efficiency of luminescent device is 6.4%, and maximum current efficiency is 21.1cdA-1, power efficiency is 18.2lm/W.
Embodiment 13：The double phosphine chlorine of feature based on 4,7- triphenylamines-dibenzothiophenes group manufactured in the present embodiment
The method and the difference of embodiment one for changing cuprous cluster compound electroluminescent material be：Described feature biphosphine ligand isWherein, described Z isDescribed cuprous halide is stannous chloride.Other with the phase of embodiment one
Together.
The double phosphine stannous chloride clusters of feature based on 4,7- triphenylamines-dibenzothiophenes group prepared by embodiment 13 are closed
The structural formula of thing electroluminescent material is：Wherein, described X is Cl；Described Z is
The double phosphines of the feature based on 4,7- triphenylamines-dibenzothiophenes group prepared using Mass Spectrometer Method embodiment 13
Stannous chloride cluster compound electroluminescent material, testing result is as follows：Exact Mass:2468.26；m/z:2473.26
(100.0%)；Elemental Analysis for C144H104Cl4Cu4N4P4S2:C,69.90；H,4.24；S,2.59.
The application test of embodiment 13：This experiment is with the difference of the application test of embodiment one：In step 4
The double phosphine chlorinations of the feature based on 4,7- triphenylamines-dibenzothiophenes group prepared by embodiment 13 are deposited with exciton barrier-layer
Cuprous cluster compound electroluminescent material, obtains thickness for 25nm luminescent layers.Other application tests with embodiment one are identical.
As can be seen from Figure 25, the double phosphines of the feature based on 4,7- triphenylamines-dibenzothiophenes group that prepared by embodiment 13
Stannous chloride cluster compound UV absorption is 280nm, and fluorescent emission is 480nm.As can be seen from Figure 28, prepared using embodiment 13
Prepared by the double phosphine stannous chloride cluster compound electroluminescent materials of the feature based on 4,7- triphenylamines-dibenzothiophenes group electroluminescent
The maximum external quantum efficiency of luminescent device is 8.1%, and maximum current efficiency is 21.1cdA-1, power efficiency is 19.5lm/W.
Embodiment 14：The double phosphine bromines of feature based on 4,7- triphenylamines-dibenzothiophenes group manufactured in the present embodiment
The method and the difference of embodiment one for changing cuprous cluster compound electroluminescent material be：Described feature biphosphine ligand isWherein, described Z isDescribed cuprous halide is cuprous bromide.Other are identical with embodiment one.
The double phosphine stannous chloride clusters of feature based on 4,7- triphenylamines-dibenzothiophenes group prepared by embodiment 14 are closed
The structural formula of thing electroluminescent material is：Wherein, described X is Br；Described Z is
The double phosphines of the feature based on 4,7- triphenylamines-dibenzothiophenes group prepared using Mass Spectrometer Method embodiment 14
Cuprous bromide cluster compound electroluminescent material, testing result is as follows：Exact Mass:2644.06；m/z:2651.05
(100.0%)；Elemental Analysis for C144H104Br4Cu4N4P4S2:C,65.21；H,3.95；S,2.42.
The application test of embodiment 14：This experiment is with the difference of the application test of embodiment one：In step 4
The double phosphine brominations of the feature based on 4,7- triphenylamines-dibenzothiophenes group prepared by embodiment 14 are deposited with exciton barrier-layer
Cuprous cluster compound electroluminescent material, obtains thickness for 25nm luminescent layers.Other application tests with embodiment one are identical.
As can be seen from Figure 26, the double phosphines of the feature based on 4,7- triphenylamines-dibenzothiophenes group that prepared by embodiment 14
Cuprous bromide cluster compound UV absorption is 280nm, and fluorescent emission is 500nm.As can be seen from Figure 29, prepared using embodiment 14
Prepared by the double phosphine cuprous bromide cluster compound electroluminescent materials of the feature based on 4,7- triphenylamines-dibenzothiophenes group electroluminescent
The maximum external quantum efficiency of luminescent device is 8.2%, and maximum current efficiency is 20.7cdA-1, power efficiency is 21.5lm/W.
Embodiment 15：The double phosphine iodine of feature based on 4,7- triphenylamines-dibenzothiophenes group manufactured in the present embodiment
The method and the difference of embodiment one for changing cuprous cluster compound electroluminescent material be：Described feature biphosphine ligand isWherein, described Z isDescribed cuprous halide is cuprous iodide.Other are identical with embodiment one.
The double phosphine cuprous iodide clusters of feature based on 4,7- triphenylamines-dibenzothiophenes group prepared by embodiment 15 are closed
The structural formula of thing electroluminescent material is：Wherein, described X is I；Described Z is
The double phosphines of the feature based on 4,7- triphenylamines-dibenzothiophenes group prepared using Mass Spectrometer Method embodiment 15
Cuprous iodide cluster compound electroluminescent material, testing result is as follows：Exact Mass:2836.00；m/z:2839.00
(100.0%)；Elemental Analysis for C144H104I4Cu4N4P4S2:C,60.90；H,3.69；S,2.26.
The application test of embodiment 15：This experiment is with the difference of the application test of embodiment one：In step 4
The double phosphine iodate of the feature based on 4,7- triphenylamines-dibenzothiophenes group prepared by embodiment 15 are deposited with exciton barrier-layer
Cuprous cluster compound electroluminescent material, obtains thickness for 25nm luminescent layers.Other application tests with embodiment one are identical.
As can be seen from Figure 27, the double phosphines of the feature based on 4,7- triphenylamines-dibenzothiophenes group that prepared by embodiment 15
Cuprous iodide cluster compound UV absorption is 280nm, and fluorescent emission is 490nm.As can be seen from Figure 30, prepared using embodiment 15
Prepared by the double phosphine cuprous iodide cluster compound electroluminescent materials of the feature based on 4,7- triphenylamines-dibenzothiophenes group electroluminescent
The maximum external quantum efficiency of luminescent device is 7.8%, and maximum current efficiency is 21.4cdA-1, power efficiency is 17.1lm/W.
Embodiment 16：Feature based on 4,7- dendroids carbazole-dibenzothiophenes group manufactured in the present embodiment is double
The method of phosphine stannous chloride cluster compound electroluminescent material is with the difference of embodiment one：Described feature biphosphine ligand isWherein, described Z isDescribed cuprous halide is stannous chloride.Other with the phase of embodiment one
Together.
The double phosphine stannous chlorides of feature based on 4,7- dendroids carbazole-dibenzothiophenes group prepared by embodiment 16
The structural formula of cluster compound electroluminescent material is：Wherein, described X is Cl；Described Z is
The feature based on 4,7- dendroids carbazole-dibenzothiophenes group prepared using Mass Spectrometer Method embodiment 16
Double phosphine stannous chloride cluster compound electroluminescent materials, testing result is as follows：Exact Mass:3476.53；m/z:3482.54
(100.0%)；Elemental Analysis for C216H136Cl4Cu4N12P4S2:C,74.48；H,3.94；S,1.84.
The application test of embodiment 16：This experiment is with the difference of the application test of embodiment one：In step 4
The double phosphines of the feature based on 4,7- dendroids carbazole-dibenzothiophenes group prepared by embodiment 16 are deposited with exciton barrier-layer
Stannous chloride cluster compound electroluminescent material, obtains thickness for 25nm luminescent layers.Other with the application test phase of embodiment one
Together.
As can be seen from Figure 31, the double phosphine stannous chloride clusters of the feature based on 4,7- dendroids carbazole-dibenzothiophenes group are closed
Thing UV absorption is 280nm, and fluorescent emission is 440nm.As can be seen from Figure 34,4, the 7- dendroid clicks for being prepared using embodiment 16
Electroluminescent device prepared by the double phosphine stannous chloride cluster compound electroluminescent materials of the feature of azoles-dibenzothiophenes group is most
Big external quantum efficiency is 9.0%, and maximum current efficiency is 20.1cdA-1, power efficiency is 27.0lm/W.
Embodiment 17：Feature based on 4,7- dendroids carbazole-dibenzothiophenes group manufactured in the present embodiment is double
The method of phosphine cuprous bromide cluster compound electroluminescent material is not both with embodiment one：Described feature biphosphine ligand isWherein, described Z isDescribed cuprous halide is cuprous bromide.Other with the phase of embodiment one
Together.
The double phosphine cuprous bromides of feature based on 4,7- dendroids carbazole-dibenzothiophenes group prepared by embodiment 17
The structural formula of cluster compound electroluminescent material is：Wherein, described X is Br；Described Z is
The feature based on 4,7- dendroids carbazole-dibenzothiophenes group prepared using Mass Spectrometer Method embodiment 17
Double phosphine cuprous bromide cluster compound electroluminescent materials, testing result is as follows：Exact Mass:3652.33；m/z:3659.33
(100.0%)；Elemental Analysis for C216H136Br4Cu4N12P4S2:C,70.86；H,3.74；S,1.75.
The application test of embodiment 17：This experiment is not both with the application test of embodiment one：Swashing in step 4
The double phosphine bromines of the feature based on 4,7- dendroids carbazole-dibenzothiophenes group prepared by embodiment 17 are deposited with sub- barrier layer
Change cuprous cluster compound electroluminescent material, obtain thickness for 25nm luminescent layers.Other application tests with embodiment one are identical.
As can be seen from Figure 32, the double phosphine cuprous bromide clusters of the feature based on 4,7- dendroids carbazole-dibenzothiophenes group are closed
Thing UV absorption is 280nm, and fluorescent emission is 490nm.As can be seen from Figure 35, using the preparation of embodiment 17 based on 4,7- branches
Electroluminescent device prepared by the double phosphine cuprous bromide cluster compound electroluminescent materials of the feature of shape carbazole-dibenzothiophenes group
Maximum external quantum efficiency be 7.5%, maximum current efficiency be 20.0cdA-1, power efficiency is 24.7lm/W.
Embodiment 18：Feature based on 4,7- dendroids carbazole-dibenzothiophenes group manufactured in the present embodiment is double
The method of phosphine cuprous iodide cluster compound electroluminescent material is with the difference of embodiment one：Described feature biphosphine ligand isWherein, described Z isDescribed cuprous halide is cuprous iodide.Other with the phase of embodiment one
Together.
The double phosphine cuprous iodides of feature based on 4,7- dendroids carbazole-dibenzothiophenes group prepared by embodiment 18
The structural formula of cluster compound electroluminescent material is：Wherein, described X is I；Described Z is
The feature based on 4,7- dendroids carbazole-dibenzothiophenes group prepared using Mass Spectrometer Method embodiment 18
Double phosphine cuprous iodide cluster compound electroluminescent materials, testing result is as follows：Exact Mass:3844.28；m/z:3848.28
(100.0%)；Elemental Analysis for C216H136I4Cu4N12P4S2:C,67.40；H,3.56；S,1.67.
The application test of embodiment 18：This experiment is with the difference of the application test of embodiment one：In step 4
The double phosphines of the feature based on 4,7- dendroids carbazole-dibenzothiophenes group prepared by embodiment 18 are deposited with exciton barrier-layer
Cuprous iodide cluster compound electroluminescent material, obtains thickness for 25nm luminescent layers.Other with the application test phase of embodiment one
Together.
As can be seen from Figure 33, the feature based on 4,7- dendroids carbazole-dibenzothiophenes group that prepared by embodiment 18
Double phosphine cuprous iodide cluster compound UV absorptions are 280nm, and fluorescent emission is 490nm.As can be seen from Figure 36, made using embodiment 18
The double phosphine cuprous iodide cluster compound electroluminescent material systems of the standby feature based on 4,7- dendroids carbazole-dibenzothiophenes group
The maximum external quantum efficiency of standby electroluminescent device is 6.9%, and maximum current efficiency is 20.9cdA-1, power efficiency is
24.2lm/W。
Embodiment 19：Work(based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group manufactured in the present embodiment
Can the method for the double phosphine stannous chloride cluster compound electroluminescent materials of property be with the difference of embodiment one：The double phosphines of described feature
Part isWherein, described Z isDescribed cuprous halide is stannous chloride.Other with reality
Apply example one identical.
The double phosphine chlorine of feature based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group prepared by embodiment 19
The structural formula for changing cuprous cluster compound electroluminescent material is：Wherein, described X is Cl；Described Z is
Using Mass Spectrometer Method embodiment 19 prepare based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group
The double phosphine stannous chloride cluster compound electroluminescent materials of feature, testing result is as follows：Exact Mass:4405.60；m/z:
4412.60 (100.0%)；Elemental Analysis for C282H272Cl4Cu4N12P4S2:C,76.75；H,6.21；S,
1.45。
The application test of embodiment 19：This experiment is with the difference of the application test of embodiment one：In step 4
The function based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group prepared by embodiment 19 is deposited with exciton barrier-layer
Property double phosphine stannous chloride cluster compound electroluminescent materials, obtain thickness for 25nm luminescent layers.Other with the application of embodiment one
Experiment is identical.
As can be seen from Figure 37, embodiment 19 prepare based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group
The double phosphine stannous chloride cluster compound UV absorptions of feature are 280nm, and fluorescent emission is 460nm.As can be seen from Figure 40, using embodiment
The double phosphine stannous chloride cluster compound electricity of 19 features based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group for preparing
The maximum external quantum efficiency of electroluminescent device prepared by electroluminescent material is 7.8%, and maximum current efficiency is 20.2cdA-1,
Power efficiency is 27.0lm/W.
Embodiment 20：Work(based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group manufactured in the present embodiment
Can the method for the double phosphine cuprous bromide cluster compound electroluminescent materials of property be with the difference of embodiment one：The double phosphines of described feature
Part isWherein, described Z isDescribed cuprous halide is cuprous bromide.Other with
Embodiment one is identical.
The double phosphine bromines of feature based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group prepared by embodiment 20
The structural formula for changing cuprous cluster compound electroluminescent material is：Wherein, described X is Br；Described Z is
Using Mass Spectrometer Method embodiment 20 prepare based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group
The double phosphine cuprous bromide cluster compound electroluminescent materials of feature, testing result is as follows：Exact Mass:4581.40；m/z:
4590.40 (100.0%)；Elemental Analysis for for C282H272Br4Cu4N12P4S2:C,73.77；H,5.97；
S,1.40。
The application test of embodiment 20：This experiment is with the difference of the application test of embodiment one：In step 4
The function based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group prepared by embodiment 20 is deposited with exciton barrier-layer
Property double phosphine cuprous bromide cluster compound electroluminescent materials, obtain thickness for 25nm luminescent layers.Other with the application of embodiment one
Experiment is identical.
As can be seen from Figure 38, the double phosphine protobromides of the feature based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group
Copper cluster UV absorption is 280nm, and fluorescent emission is 460nm.As can be seen from Figure 41, with the preparation of embodiment 20 based on 4,7-
Electricity prepared by the double phosphine cuprous bromide cluster compound electroluminescent materials of the feature of dendroid tert-butyl carbazole-dibenzothiophenes group
The maximum external quantum efficiency of electroluminescence device is 7.7%, and maximum current efficiency is 20.0cdA-1, power efficiency is 27.7lm/
W。
Embodiment 21：It is manufactured in the present embodiment based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group
The method of the double phosphine cuprous iodide cluster compound electroluminescent materials of feature is with the difference of embodiment one：Described feature is double
Phosphine ligands areWherein, described Z isDescribed cuprous halide is cuprous iodide.Other with
Embodiment one is identical.
The double phosphines of feature based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group prepared by embodiment 21
The structural formula of cuprous iodide cluster compound electroluminescent material is：Wherein, described X is I；Described Z is
Using the preparation of Mass Spectrometer Method embodiment 21 based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group
The double phosphine cuprous iodide cluster compound electroluminescent materials of feature, testing result is as follows：Exact Mass:4773.34；m/z:
4778.35 (100.0%)；Elemental Analysis for C282H272I4Cu4N12P4S2:C,70.87；H,5.74；S,
1.34。
The application test of embodiment 21：This experiment is with the difference of the application test of embodiment one：In step 4
Be deposited with prepared by embodiment 21 on exciton barrier-layer based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group
The double phosphine cuprous iodide cluster compound electroluminescent materials of feature, obtain thickness for 25nm luminescent layers.Other with embodiment one
Application test is identical.
As can be seen from Figure 39, the iodate of the double phosphines of the feature based on 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group is sub-
Copper cluster UV absorption is 280nm, and fluorescent emission is 495nm.As can be seen from Figure 42, using embodiment 21 prepare based on
It is prepared by the double phosphine cuprous iodide cluster compound electroluminescent materials of the feature of 4,7- dendroids tert-butyl carbazole-dibenzothiophenes group
Electroluminescent device maximum external quantum efficiency be 7.5%, maximum current efficiency be 20.1cdA-1, power efficiency is
23.7lm/W。
Embodiment 22：It is manufactured in the present embodiment based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group
The method of the double phosphine stannous chloride cluster compound electroluminescent materials of feature is with the difference of embodiment one：Described feature is double
Phosphine ligands areWherein, described Z isDescribed cuprous halide is stannous chloride.Other with reality
Apply example one identical.
The double phosphines of feature based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group prepared by embodiment 22
The structural formula of stannous chloride cluster compound electroluminescent material is：Wherein, described X is Cl；Described Z is
Using the preparation of Mass Spectrometer Method embodiment 22 based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group
The double phosphine stannous chloride cluster compound electroluminescent materials of feature, testing result is as follows：Exact Mass:3492.66；m/z:
3498.66 (100.0%)；Elemental Analysis for C216H152Cl4Cu4N12P4S2:C,74.13；H,4.38；S,
1.83。
The application test of embodiment 22：This experiment is with the difference of the application test of embodiment one：In step 4
Be deposited with prepared by embodiment 22 on exciton barrier-layer based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group
The double phosphine stannous chloride cluster compound electroluminescent materials of feature, obtain thickness for 25nm luminescent layers.Other with embodiment one
Application test is identical.
As can be seen from Figure 43, embodiment 22 prepare based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group
The double phosphine stannous chloride cluster compound electroluminescent material UV absorptions of feature be 280nm, fluorescent emission is 470nm.From Figure 46
Understand, the feature based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group prepared using embodiment 22 is double
The maximum external quantum efficiency of electroluminescent device prepared by phosphine stannous chloride cluster compound electroluminescent material is 8.3%, maximum electricity
Stream efficiency is 20.6cdA-1, power efficiency is 27.7lm/W.
Embodiment 23：It is manufactured in the present embodiment based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group
The method of the double phosphine cuprous bromide cluster compound electroluminescent materials of feature is with the difference of embodiment one：Described feature is double
Phosphine ligands areWherein, described Z isDescribed cuprous halide is cuprous bromide.Other with reality
Apply example one identical.
The double phosphines of feature based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group prepared by embodiment 23
The structural formula of cuprous bromide cluster compound electroluminescent material is：Wherein, described X is Br；Described Z is
Using the preparation of Mass Spectrometer Method embodiment 23 based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group
The double phosphine cuprous bromide cluster compound electroluminescent materials of feature, testing result is as follows：Exact Mass:3668.46；m/z:
3676.46 (100.0%)；Elemental Analysis for C216H152Br4Cu4N12P4S2:C,70.55；H,4.17；S,
1.74。
The application test of embodiment 23：This experiment is with the difference of the application test of embodiment one：In step 4
Be deposited with prepared by embodiment 23 on exciton barrier-layer based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group
The double phosphine cuprous bromide cluster compound electroluminescent materials of feature, obtain thickness for 25nm luminescent layers.Other with embodiment one
Application test is identical.
As can be seen from Figure 44, embodiment 23 prepare based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group
The double phosphine cuprous bromide cluster compound electroluminescent material UV absorptions of feature be 280nm, fluorescent emission is 500nm.From Figure 47
Understand, the feature based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group prepared using embodiment 23 is double
The maximum external quantum efficiency of electroluminescent device prepared by phosphine cuprous bromide cluster compound electroluminescent material is 7.9%, maximum electricity
Stream efficiency is 20.8cdA-1, power efficiency is 22.3lm/W.
Embodiment 24：It is manufactured in the present embodiment based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group
The method of the double phosphine cuprous iodide cluster compound electroluminescent materials of feature is with the difference of embodiment one：Described feature is double
Phosphine ligands areWherein, described Z isDescribed cuprous halide is cuprous iodide.Other with
Embodiment one is identical.
The double phosphines of feature based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group prepared by embodiment 24
The structural formula of cuprous iodide cluster compound electroluminescent material is：Wherein, described X is I；Described Z is
Using the preparation of Mass Spectrometer Method embodiment 24 based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group
The double phosphine cuprous iodide cluster compound electroluminescent materials of feature, testing result is as follows：Exact Mass:3860.40；m/z:
3864.41 (100.0%)；Elemental Analysis for C216H152I4Cu4N12P4S2:C,67.12；H,3.96；S,
1.66。
The application test of embodiment 24：This experiment is with the difference of the application test of embodiment one：In step 4
Be deposited with prepared by embodiment 24 on exciton barrier-layer based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group
The double phosphine cuprous iodide cluster compound electroluminescent materials of feature, obtain thickness for 25nm luminescent layers.Other with embodiment one
Application test is identical.
As can be seen from Figure 45, embodiment 24 prepare based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group
The double phosphine cuprous iodide cluster compound electroluminescent material UV absorptions of feature be 282nm, fluorescent emission is 490nm.From Figure 48
Understand, the feature based on 4,7- dendroids carbazole diphenylamines-dibenzothiophenes group prepared using embodiment 24 is double
The maximum external quantum efficiency of electroluminescent device prepared by phosphine cuprous iodide cluster compound electroluminescent material is 8%, maximum current
Efficiency is 21.4cdA-1, power efficiency is 26.4lm/W.
Embodiment 25：It is manufactured in the present embodiment based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group
The method of the double phosphine stannous chloride cluster compound electroluminescent materials of feature is with the difference of embodiment one：Described feature is double
Phosphine ligands areWherein, described Z isDescribed cuprous halide is stannous chloride.Other with
Embodiment one is identical.
The double phosphines of feature based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group prepared by embodiment 25
The structural formula of stannous chloride cluster compound electroluminescent material is：Wherein, described X is Cl；Described Z is
Using the preparation of Mass Spectrometer Method embodiment 25 based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group
The double phosphine stannous chloride cluster compound electroluminescent materials of feature, testing result is as follows：Exact Mass:4100.91；m/z:
4106.91 (100.0%)；Elemental Analysis for C264H184Cu4Cl4N12P4S2:C,77.18；H,4.51；S,
1.56。
The application test of embodiment 25：This experiment is with the difference of the application test of embodiment one：In step 4
Be deposited with prepared by embodiment 25 on exciton barrier-layer based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group
The double phosphine stannous chloride cluster compound electroluminescent materials of feature, obtain thickness for 25nm luminescent layers.Other with embodiment one
Application test is identical.
As can be seen from Figure 49, embodiment 25 prepare based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group
The double phosphine stannous chloride cluster compound electroluminescent material UV absorptions of feature be 280nm, fluorescent emission is 465nm.From Figure 52
Understand, the feature based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group prepared using embodiment 25 is double
The maximum external quantum efficiency of electroluminescent device prepared by phosphine stannous chloride cluster compound electroluminescent material is 7.8%, maximum electricity
Stream efficiency is 20.1cdA-1, power efficiency is 20.0lm/W.
Embodiment 26：It is manufactured in the present embodiment based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group
The method of the double phosphine cuprous bromide cluster compound electroluminescent materials of feature is with the difference of embodiment one：Described feature is double
Phosphine ligands areWherein, described Z isDescribed cuprous halide is cuprous bromide.Other are equal
It is identical with embodiment one.
The double phosphines of feature based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group prepared by embodiment 26
The structural formula of cuprous bromide cluster compound electroluminescent material is：Wherein, described X is Br；Described Z is
Using the preparation of Mass Spectrometer Method embodiment 26 based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group
The double phosphine cuprous bromide cluster compound electroluminescent materials of feature, testing result is as follows：Exact Mass:4276.71；m/z:
4284.71 (100.0%)；Elemental Analysis for C264H184Cu4Br4N12P4S2:C,73.98；H,4.33；S,
1.50。
The application test of embodiment 26：This experiment is with the difference of the application test of embodiment one：In step 4
Be deposited with prepared by embodiment 26 on exciton barrier-layer based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group
The double phosphine cuprous bromide cluster compound electroluminescent materials of feature, obtain thickness for 25nm luminescent layers.Other with embodiment one
Application test is identical.
As can be seen from Figure 50, embodiment 26 prepare based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group
The double phosphine cuprous bromide cluster compound electroluminescent material UV absorptions of feature be 280nm, fluorescent emission is 505nm.From Figure 53
Understand, the feature based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group prepared using embodiment 26 is double
The maximum external quantum efficiency of electroluminescent device prepared by phosphine cuprous bromide cluster compound electroluminescent material is 7.5%, maximum electricity
Stream efficiency is 20.0cdA-1, power efficiency is 25.2lm/W.
Embodiment 27：It is manufactured in the present embodiment based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group
The method of the double phosphine cuprous iodide cluster compound electroluminescent materials of feature is with the difference of embodiment one：Described feature is double
Phosphine ligands areWherein, described Z isDescribed cuprous halide is cuprous iodide.Other with
Embodiment one is identical.
The double phosphines of feature based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group prepared by embodiment 27
The structural formula of cuprous iodide cluster compound electroluminescent material is：Wherein, described X is I；Described Z is
Using the preparation of Mass Spectrometer Method embodiment 27 based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group
The double phosphine cuprous iodide cluster compound electroluminescent materials of feature, testing result is as follows：
Exact Mass:4468.65；m/z:4472.66 (100.0%)；Elemental Analysis for
C264H184Cu4I4N12P4S2:C,70.87；H,4.15；S,1.43.
The application test of embodiment 27：This experiment is with the difference of the application test of embodiment one：In step 4
Be deposited with prepared by embodiment 27 on exciton barrier-layer based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group
The double phosphine cuprous iodide cluster compound electroluminescent materials of feature, obtain thickness for 25nm luminescent layers.Other with embodiment one
Application test is identical.
As we know from Figure 51, embodiment 27 prepare based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group
The double phosphine cuprous iodide cluster compound electroluminescent material UV absorptions of feature be 282nm, fluorescent emission is 490nm.From Figure 54
Understand, the feature based on 4,7- dendroids carbazole triphenylamine-dibenzothiophenes group prepared using embodiment 27 is double
The maximum external quantum efficiency of electroluminescent device prepared by phosphine cuprous iodide cluster compound electroluminescent material is 8%, maximum current
Efficiency is 20.7cdA-1, power efficiency is 24.8lm/W.
Knowable to Figure 55,56,57, electroluminescent peak value is respectively 505nm, 510nm, 515nm；Can from Figure 58,59,60
Know, electroluminescent peak value is respectively 505nm, 509nm, 500nm；Knowable to Figure 61,62,63, electroluminescent peak value is respectively
505nm、510nm、515nm；Knowable to Figure 64,65,66, electroluminescent peak value is respectively 550nm, 570nm, 520nm；From figure
67th, 68,69 understand that electroluminescent peak value is respectively 510nm, 509nm, 515nm；Knowable to Figure 70,71,72, electroluminescent peak
Value is respectively 520nm, 520nm, 522nm；Knowable to Figure 73,74,75, electroluminescent peak value be respectively 560m, 580nm,
540nm；Knowable to Figure 76,77,78, electroluminescent peak value is respectively 515nm, 510nm, 515nm；Knowable to Figure 79,80,81,
Electroluminescent peak value is respectively 550nm, 540nm, 520nm.
Claims (10)
1. a kind of double phosphine copper cluster electroluminescent materials of feature based on dibenzothiophenes group, it is characterised in that Yi Zhongji
It is in the structural formula of the double phosphine copper cluster electroluminescent materials of the feature of dibenzothiophenes group：
Wherein, described X is Cl, Br or I；Described Z be H, Described PPh2Structure be
2. double phosphine copper cluster electroluminescent materials of a kind of feature based on dibenzothiophenes group as claimed in claim 1
Preparation method, it is characterised in that a kind of double phosphine copper cluster electroluminescent materials of feature based on dibenzothiophenes group
What preparation method was specifically realized by the following steps：
By feature biphosphine ligand, cuprous halide and dichloromethane mix, then temperature be 40 DEG C~45 DEG C at react 10h~
15h, reuses Rotary Evaporators and is spin-dried for, and obtains solid matter；Using the mixed liquor of dichloromethane and petroleum ether for eluent enters
Row column chromatography is purified, and obtains the double phosphine copper cluster electroluminescent materials of the feature based on dibenzothiophenes group；
Described feature biphosphine ligand is (0.5~3) with the amount ratio of the material of cuprous halide:1；
The amount of the material of described feature biphosphine ligand is 1mmol with the volume ratio of dichloromethane:(3mL~10mL)；
Described feature biphosphine ligand isWherein, described Z be H, Described PPh2Structure be
3. double phosphine copper cluster electroluminescence materials of a kind of feature based on dibenzothiophenes group according to claim 2
The preparation method of material, it is characterised in that the volume of dichloromethane and petroleum ether in described dichloromethane and the mixed liquor of petroleum ether
Than being 1:20.
4. double phosphine copper cluster electroluminescence materials of a kind of feature based on dibenzothiophenes group according to claim 2
The preparation method of material, it is characterised in that described feature biphosphine ligand is (1~3) with the amount ratio of the material of cuprous halide:1.
5. double phosphine copper cluster electroluminescence materials of a kind of feature based on dibenzothiophenes group according to claim 2
The preparation method of material, it is characterised in that described feature biphosphine ligand is (2~3) with the amount ratio of the material of cuprous halide:1.
6. double phosphine copper cluster electroluminescence materials of a kind of feature based on dibenzothiophenes group according to claim 2
The preparation method of material, it is characterised in that the amount of material of described feature biphosphine ligand is with the volume ratio of dichloromethane
1mmol:(3mL~5mL).
7. double phosphine copper cluster electroluminescence materials of a kind of feature based on dibenzothiophenes group according to claim 2
The preparation method of material, it is characterised in that the amount of material of described feature biphosphine ligand is with the volume ratio of dichloromethane
1mmol:(5mL~10mL).
8. double phosphine copper cluster electroluminescence materials of a kind of feature based on dibenzothiophenes group according to claim 2
The preparation method of material, it is characterised in that described cuprous halide is stannous chloride, cuprous bromide or cuprous iodide.
9. double phosphine copper cluster electroluminescence materials of a kind of feature based on dibenzothiophenes group according to claim 2
The preparation method of material, it is characterised in that mix feature biphosphine ligand, cuprous halide and dichloromethane, then be 40 DEG C in temperature
10h~13h is reacted at~45 DEG C, Rotary Evaporators is reused and is spin-dried for, obtain solid matter；Use dichloromethane and petroleum ether
Mixed liquor carries out column chromatography purifying for eluent, obtains the double phosphine electroluminescent hairs of copper cluster of the feature based on dibenzothiophenes group
Luminescent material.
10. double phosphine copper cluster electroluminescence materials of a kind of feature based on dibenzothiophenes group as claimed in claim 1
A kind of application of material, it is characterised in that the double phosphine copper cluster electroluminescent material conducts of feature based on dibenzothiophenes group
Emitting layer material is applied in electroluminescent device.
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| CN106831865B (en) | 2019-01-08 |
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