CN106831865B - A kind of double phosphine copper cluster electroluminescent materials of functionality based on dibenzothiophenes group and preparation method and application - Google Patents
A kind of double phosphine copper cluster electroluminescent materials of functionality based on dibenzothiophenes group and preparation method and application Download PDFInfo
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- CN106831865B CN106831865B CN201710081637.1A CN201710081637A CN106831865B CN 106831865 B CN106831865 B CN 106831865B CN 201710081637 A CN201710081637 A CN 201710081637A CN 106831865 B CN106831865 B CN 106831865B
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- dibenzothiophenes group
- double phosphine
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- 239000000463 material Substances 0.000 title claims abstract description 292
- 238000002360 preparation method Methods 0.000 title claims abstract description 166
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical group C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 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 48
- 150000004820 halides Chemical class 0.000 claims abstract description 39
- 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
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000003480 eluent Substances 0.000 claims abstract description 5
- 238000005401 electroluminescence Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 6
- 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 227
- 238000000034 method Methods 0.000 abstract description 59
- 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
- 238000010791 quenching Methods 0.000 abstract description 2
- 230000000171 quenching effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000004440 column chromatography Methods 0.000 abstract 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 369
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 191
- 238000012360 testing method Methods 0.000 description 132
- 241000555268 Dendroides Species 0.000 description 107
- -1 4,7- di-t-butyl carbazole-dibenzothiophenes group Chemical group 0.000 description 95
- 235000011150 stannous chloride Nutrition 0.000 description 67
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 64
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 64
- 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 compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 61
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 61
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 61
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 61
- 239000001119 stannous chloride Substances 0.000 description 61
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 54
- 239000010949 copper Substances 0.000 description 40
- 230000009102 absorption Effects 0.000 description 36
- 238000001228 spectrum Methods 0.000 description 34
- 230000008859 change Effects 0.000 description 28
- 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 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 22
- 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
- 229910052802 copper Inorganic materials 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 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
- RRLCRPBPKLRKMD-UHFFFAOYSA-N [PH4+].I(=O)(=O)[O-] Chemical compound [PH4+].I(=O)(=O)[O-] RRLCRPBPKLRKMD-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 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
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 2
- 150000004699 copper complex Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005525 hole transport Effects 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
- 238000007740 vapor deposition Methods 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
- 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
- 230000005540 biological transmission Effects 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
- 239000008391 electroluminescent agent Substances 0.000 description 1
- 238000010828 elution 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
- 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
- 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
- 239000000243 solution Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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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Abstract
A kind of double phosphine copper cluster electroluminescent materials of functionality and preparation method and application based on dibenzothiophenes group, it is related to a kind of electroluminescent material and preparation method and application.The invention aims to solve the disadvantage that existing cluster compound electroluminescent material photobleaching is strong, carrier transport ability is weak, stability of photoluminescence is poor, self-absorption is strong and mulecular luminescence quenching.A kind of structural formula of the double phosphine copper cluster electroluminescent materials of functionality based on dibenzothiophenes group are as follows:Method: functional biphosphine ligand, cuprous halide and methylene chloride are mixed, reaction, then are spin-dried for, and solid matter is obtained；The use of the mixed liquor of methylene chloride and petroleum ether is that eluent progress column chromatography is purified, that is, completes.A kind of double phosphine copper cluster electroluminescent materials of functionality based on dibenzothiophenes group are applied in electroluminescent device as emitting layer material.The present invention can get a kind of double phosphine copper cluster electroluminescent materials of the functionality based on dibenzothiophenes group.
Description
Technical field
The present invention relates to a kind of electroluminescent material and preparation method and application.
Background technique
Organic electroluminescent LED is referred to as third generation plane and shows and lighting engineering, in terms of have
Advantage outstanding.The complex that metal and organic molecule are formed is due to its unique orbit coupling mode, so that complex has
Phosphorescent or fluorescence characteristic, but due to the heavy metals such as traditional complex material multi-purpose greatly gold, platinum, these metal storages
Scarcity, exploitation is difficult, involves great expense, thus it is desirable to it is more cheap, be easier to obtain and nontoxic metal replace it is valuable
Metal, and copper complex, environmental-friendly since its is low in cost, shining has the characteristics such as hot activation delayed fluorescence, gradually becomes
The favorable substitutes of precious metal complex.
In copper complex, cluster compound still has many performance deficiencies, if carrier transport ability is weak, luminous intensity is low,
The problems such as molecule self-absorption is serious, luminescence queenching.In addition, the disadvantages of dissolubility of cluster compound is poor, cluster structure is easily broken, increases
The difficulty of its reprocessing.For example, compound dissolubility synthesized by Braga seminar is poor, and during vapor deposition, molecule
Cluster structure fracture leads to device vapor deposition failure.It is therefore desirable to obtain a kind of cluster compound with excellent performance: relatively strong
Carrier transport ability, high luminous intensity, preferable dissolubility, stabilization and it is controllable shine, big Stokes shift,
The features such as easy to process.
Summary of the invention
The invention aims to solve, existing cluster compound electroluminescent material photobleaching is strong, carrier transport ability
Weak, the shortcomings that stability of photoluminescence is poor, self-absorption is strong and mulecular luminescence quenches, and provide a kind of based on dibenzothiophenes group
Functional double phosphine copper cluster electroluminescent materials and preparation method and application.
A kind of structural formula of the double phosphine copper cluster electroluminescent materials of functionality based on dibenzothiophenes group are as follows:Wherein, the X is Cl, Br or I；The Z be H, The PPh2Structure be
The principle of the present invention and advantage:
One, the double phosphine copper cluster electroluminescent materials of the functionality prepared by the present invention based on dibenzothiophenes group are available
In preparing electroluminescent device；Entire molecule has big Stokes shift, high fluorescence intensity, adjustable fluorescent emission
With high stability of photoluminescence, the advantages that stronger carrier transport, the performance with luminescence generated by light, mechanoluminescence is also had both
The characteristics of electroluminescent；Effective solution copper luminescent material light it is Bleachability it is strong, carrier transport ability is weak, stability of photoluminescence
Difference, shine the disadvantages of uncontrollable, self-absorption is strong, molecule quenching；
Two, the double phosphine copper cluster electroluminescent materials of the functionality prepared by the present invention based on dibenzothiophenes group have
The luminous characteristics such as mechanoluminescence, luminescence generated by light, electroluminescent, the prepared by the method function based on dibenzothiophenes group
Property double phosphine copper cluster electroluminescent material preparation luminescent device, current efficiency maximum value is 21.5cdA-1, outer quantum
Maximum efficiency is 9.8%, and power efficiency maximum value is 27.7lm/W；
Three, the double phosphine copper cluster electroluminescent materials of the functionality prepared by the present invention based on dibenzothiophenes group have
Preferable stability of photoluminescence, is not likely to produce photobleaching；
Four, the double phosphine copper cluster electroluminescent materials of the functionality prepared by the present invention based on dibenzothiophenes group shine
210nm is reached with biggish Stokes shift；
Five, the double phosphine copper cluster electroluminescent material current-carrying of the functionality prepared by the present invention based on dibenzothiophenes group
Sub- transmittability is stronger；
Six, present invention uses functional double phosphine groups as ligand, has more excellent luminescent properties；
Seven, the double phosphine copper cluster electroluminescent materials of the prepared by the method functionality based on dibenzothiophenes group
The external quantum efficiency of the luminescent device of preparation has a good thermodynamic stability up to 20.0%, and cracking temperature is 290 DEG C~
320 DEG C, while the luminous efficiency and brightness of electroluminescent organic material are improved, present invention is mainly applied to organic electroluminescents
In diode component.The present invention can get a kind of double phosphine copper cluster electroluminescence materials of the functionality based on dibenzothiophenes group
Material.
Detailed description of the invention
Fig. 1 is the electroluminescent hair of the double phosphine stannous chloride cluster compounds of functionality based on dibenzothiophenes group prepared by embodiment one
Luminescent material is dissolved in the curve of spectrum in methylene chloride, and " ■ " is ultra-violet absorption spectrum curve in Fig. 1, and " " is fluorescence emission spectrum
Curve；
Fig. 2 is the electroluminescent hair of the double phosphine cuprous bromide cluster compounds of functionality based on dibenzothiophenes group prepared by embodiment two
Luminescent material is dissolved in the curve of spectrum in methylene chloride, and " ■ " is ultra-violet absorption spectrum curve in Fig. 2, and " " is fluorescence emission spectrum
Curve；
Fig. 3 is the electroluminescent hair of the double phosphine cuprous iodide cluster compounds of functionality based on dibenzothiophenes group prepared by embodiment three
Luminescent material is dissolved in the curve of spectrum in methylene chloride, 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 functionality based on dibenzothiophenes group prepared using embodiment one
The efficiency chart of the electroluminescent device of electroluminescent material preparation, 1 is current efficiency-brightness curve in Fig. 4, and 2 is bright for power efficiency-
It writes music line, 3 be external quantum efficiency-brightness curve；
Fig. 5 is the double phosphine cuprous bromide cluster compound electricity of the functionality based on dibenzothiophenes group prepared using embodiment two
The efficiency chart of the electroluminescent device of electroluminescent material preparation, 1 is current efficiency-brightness curve in Fig. 5, and 2 is bright for power efficiency-
It writes music line, 3 be external quantum efficiency-brightness curve；
Fig. 6 is the double phosphine cuprous iodide cluster compound electricity of the functionality based on dibenzothiophenes group prepared using embodiment three
The efficiency chart of the electroluminescent device of electroluminescent material preparation, 1 is current efficiency-brightness curve in Fig. 6, and 2 is bright for power efficiency-
It writes music line, 3 be external quantum efficiency-brightness curve；
Fig. 7 is example IV preparation based on the functional double phosphine stannous chlorides of bis- carbazoles of 4,7--dibenzothiophenes group
Cluster compound electroluminescent material is dissolved in the curve of spectrum in methylene chloride, and " ■ " is ultra-violet absorption spectrum curve in Fig. 7, and " " is
Fluorescence emission spectral curve；
Fig. 8 is the preparation of embodiment five based on the functional double phosphine cuprous bromides of bis- carbazoles of 4,7--dibenzothiophenes group
Cluster compound electroluminescent material is dissolved in the curve of spectrum in methylene chloride, and " ■ " is ultra-violet absorption spectrum curve in Fig. 8, and " " is
Fluorescence emission spectral curve；
Fig. 9 is the preparation of embodiment six based on the functional double phosphine cuprous iodides of bis- carbazoles of 4,7--dibenzothiophenes group
Cluster compound electroluminescent material is dissolved in the curve of spectrum in methylene chloride, and " ■ " is ultra-violet absorption spectrum curve in Fig. 9, and " " is
Fluorescence emission spectral curve；
Figure 10 is using four preparation of implementation based on the functional double phosphine protochlorides of bis- carbazoles of 4,7--dibenzothiophenes group
The efficiency chart of the electroluminescent device of copper cluster electroluminescent material preparation, 1 is current efficiency-brightness curve in Figure 10, and 2 are
Power efficiency-brightness curve, 3 be external quantum efficiency-brightness curve；
Figure 11 is using five preparation of implementation based on the functional double phosphine protobromides of bis- carbazoles of 4,7--dibenzothiophenes group
The efficiency chart of the electroluminescent device of copper cluster electroluminescent material preparation, 1 is current efficiency-brightness curve in Figure 11, and 2 are
Power efficiency-brightness curve, 3 be external quantum efficiency-brightness curve；
Figure 12 is to utilize the sub- based on the functional double phosphine iodate of bis- carbazoles of 4,7--dibenzothiophenes group of six preparation of implementation
The efficiency chart of the electroluminescent device of copper cluster electroluminescent material preparation, 1 is current efficiency-brightness curve in Figure 12, and 2 are
Power efficiency-brightness curve, 3 be external quantum efficiency-brightness curve；
Figure 13 is the preparation of embodiment seven based on the functional double phosphine chlorine of 4,7- di-t-butyl carbazole-dibenzothiophenes group
Change the curve of spectrum that cuprous cluster compound electroluminescent material is dissolved in methylene chloride, " ■ " is that ultra-violet absorption spectrum is bent in Figure 13
Line, " " are fluorescence emission spectral curve；
Figure 14 is the preparation of embodiment eight based on the functional double phosphine bromines of 4,7- di-t-butyl carbazole-dibenzothiophenes group
Change the curve of spectrum that cuprous cluster compound electroluminescent material is dissolved in methylene chloride, " ■ " is that ultra-violet absorption spectrum is bent in Figure 14
Line, " " are fluorescence emission spectral curve；
Figure 15 is the preparation of embodiment nine based on the functional double phosphine iodine of 4,7- di-t-butyl carbazole-dibenzothiophenes group
Change the curve of spectrum that cuprous cluster compound electroluminescent material is dissolved in methylene chloride, " ■ " is that ultra-violet absorption spectrum is bent in Figure 15
Line, " " are fluorescence emission spectral curve；
Figure 16 is using seven preparation of implementation based on the functional double phosphine chlorine of 4,7- di-t-butyl carbazole-dibenzothiophenes group
Change the efficiency chart of the electroluminescent device of cuprous cluster compound electroluminescent material preparation, 1 is bent for current efficiency-brightness in Figure 16
Line, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 17 is to be prepared using embodiment eight based on 4,7- di-t-butyl carbazole-dibenzothiophenes group functional pair
The efficiency chart of the electroluminescent device of phosphine cuprous bromide cluster compound electroluminescent material preparation, 1 is current efficiency-brightness in Figure 17
Curve, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 18 is to be prepared using embodiment nine based on 4,7- di-t-butyl carbazole-dibenzothiophenes group functional pair
The efficiency chart of the electroluminescent device of phosphine cuprous iodide cluster compound electroluminescent material preparation, 1 is current efficiency-brightness in Figure 18
Curve, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 19 is the preparation of embodiment ten based on the functional double phosphine stannous chlorides of 4,7- diphenylamines-dibenzothiophenes group
Cluster compound electroluminescent material is dissolved in the curve of spectrum in methylene chloride, and " ■ " is ultra-violet absorption spectrum curve, " " in Figure 19
For fluorescence emission spectral curve；
Figure 20 is the preparation of embodiment 11 based on the functional double phosphine protobromides of 4,7- diphenylamines-dibenzothiophenes group
Copper cluster electroluminescent material is dissolved in the curve of spectrum in methylene chloride, and " ■ " is ultra-violet absorption spectrum curve in Figure 20,
" " is fluorescence emission spectral curve；
Figure 21 is the sub- based on the functional double phosphine iodate of 4,7- diphenylamines-dibenzothiophenes group of the preparation of embodiment 12
Copper cluster electroluminescent material is dissolved in the curve of spectrum in methylene chloride, and " ■ " is ultra-violet absorption spectrum curve in Figure 21,
" " is fluorescence emission spectral curve；
Figure 22 is to be prepared using embodiment ten based on the functional double phosphine chlorinations of 4,7- diphenylamines-dibenzothiophenes group
The efficiency chart of the electroluminescent device of cuprous cluster compound electroluminescent material preparation, 1 is current efficiency-brightness curve in Figure 22,2
It is external quantum efficiency-brightness curve for power efficiency-brightness curve, 3；
Figure 23 is to be prepared using embodiment 11 based on the functional double phosphine bromines of 4,7- diphenylamines-dibenzothiophenes group
Change the efficiency chart of the electroluminescent device of cuprous cluster compound electroluminescent material preparation, 1 is bent for current efficiency-brightness in Figure 23
Line, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 24 is to be prepared using embodiment 12 based on the functional double phosphine iodine of 4,7- diphenylamines-dibenzothiophenes group
Change the efficiency chart of the electroluminescent device of cuprous cluster compound electroluminescent material preparation, 1 is bent for current efficiency-brightness in Figure 24
Line, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 25 is the preparation of embodiment 13 based on the functional double phosphine protochlorides of 4,7- triphenylamine-dibenzothiophenes group
Copper cluster electroluminescent material is dissolved in the curve of spectrum in methylene chloride, and " ■ " is ultra-violet absorption spectrum curve in Figure 25,
" " is fluorescence emission spectral curve；
Figure 26 is the preparation of embodiment 14 based on the functional double phosphine protobromides of 4,7- triphenylamine-dibenzothiophenes group
Copper cluster electroluminescent material is dissolved in the curve of spectrum in methylene chloride, and " ■ " is ultra-violet absorption spectrum curve in Figure 26,
" " is fluorescence emission spectral curve；
Figure 27 is the sub- based on the functional double phosphine iodate of 4,7- triphenylamine-dibenzothiophenes group of the preparation of embodiment 15
Copper cluster electroluminescent material is dissolved in the curve of spectrum in methylene chloride, and " ■ " is ultra-violet absorption spectrum curve in Figure 27,
" " is fluorescence emission spectral curve；
Figure 28 is to be prepared using embodiment 13 based on the functional double phosphine chlorine of 4,7- triphenylamine-dibenzothiophenes group
Change the efficiency chart of the electroluminescent device of cuprous cluster compound electroluminescent material preparation, 1 is bent for current efficiency-brightness in Figure 28
Line, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 29 is to be prepared using embodiment 14 based on the functional double phosphine bromines of 4,7- triphenylamine-dibenzothiophenes group
Change the efficiency chart of the electroluminescent device of cuprous cluster compound electroluminescent material preparation, 1 is bent for current efficiency-brightness in Figure 29
Line, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 30 is to be prepared using embodiment 15 based on the functional double phosphine iodine of 4,7- triphenylamine-dibenzothiophenes group
Change the efficiency chart of the electroluminescent device of cuprous cluster compound electroluminescent material preparation, 1 is bent for current efficiency-brightness in Figure 30
Line, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 31 is the preparation of embodiment 16 based on the functional double phosphine chlorine of 4,7- dendroid carbazole-dibenzothiophenes group
Change the curve of spectrum that cuprous cluster compound electroluminescent material is dissolved in methylene chloride, " ■ " is that ultra-violet absorption spectrum is bent in Figure 31
Line, " " are fluorescence emission spectral curve；
Figure 32 is the preparation of embodiment 17 based on the functional double phosphine bromines of 4,7- dendroid carbazole-dibenzothiophenes group
Change the curve of spectrum that cuprous cluster compound electroluminescent material is dissolved in methylene chloride, " ■ " is that ultra-violet absorption spectrum is bent in Figure 32
Line, " " are fluorescence emission spectral curve；
Figure 33 is the preparation of embodiment 18 based on the functional double phosphine iodine of 4,7- dendroid carbazole-dibenzothiophenes group
Change the curve of spectrum that cuprous cluster compound electroluminescent material is dissolved in methylene chloride, " ■ " is that ultra-violet absorption spectrum is bent in Figure 33
Line, " " are fluorescence emission spectral curve；
Figure 34 is to be prepared using embodiment 16 based on 4,7- dendroid carbazole-dibenzothiophenes group functional pair
The efficiency chart of the electroluminescent device of phosphine stannous chloride cluster compound electroluminescent material preparation, 1 is current efficiency-brightness in Figure 34
Curve, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 35 is to be prepared using embodiment 17 based on 4,7- dendroid carbazole-dibenzothiophenes group functional pair
The efficiency chart of the electroluminescent device of phosphine cuprous bromide cluster compound electroluminescent material preparation, 1 is current efficiency-brightness in Figure 35
Curve, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 36 is to be prepared using embodiment 18 based on 4,7- dendroid carbazole-dibenzothiophenes group functional pair
The efficiency chart of the electroluminescent device of phosphine cuprous iodide cluster compound electroluminescent material preparation, 1 is current efficiency-brightness in Figure 36
Curve, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 37 is the preparation of embodiment 19 based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group functionality
Double phosphine stannous chloride cluster compound electroluminescent materials are dissolved in the curve of spectrum in methylene chloride, and " ■ " is UV absorption light in Figure 37
Spectral curve, " " are fluorescence emission spectral curve；
Figure 38 is the preparation of embodiment 20 based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group functionality
Double phosphine cuprous bromide cluster compound electroluminescent materials are dissolved in the curve of spectrum in methylene chloride, and " ■ " is UV absorption light in Figure 38
Spectral curve, " " are fluorescence emission spectral curve；
Figure 39 is the preparation of embodiment 21 based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group function
Property double phosphine cuprous iodide cluster compound electroluminescent material be dissolved in the curve of spectrum in methylene chloride, " ■ " is UV absorption in Figure 39
The curve of spectrum, " " are fluorescence emission spectral curve；
Figure 40 is to be prepared using embodiment 19 based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group function
Can the double phosphine stannous chloride cluster compound electroluminescent materials preparations of property electroluminescent device efficiency chart, 1 imitates for electric current in Figure 40
Rate-brightness curve, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 41 is to be prepared using embodiment 20 based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group function
Can the double phosphine cuprous bromide cluster compound electroluminescent materials preparations of property electroluminescent device efficiency chart, 1 imitates for electric current in Figure 41
Rate-brightness curve, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 42 is to be prepared using embodiment 21 based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group
The efficiency chart of the electroluminescent device of functional double phosphine cuprous iodide cluster compound electroluminescent materials preparation, 1 is electric current in Figure 42
Ciency-luminance curve, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 43 is the preparation of embodiment 22 based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group function
Property double phosphine stannous chloride cluster compound electroluminescent material be dissolved in the curve of spectrum in methylene chloride, " ■ " is UV absorption in Figure 43
The curve of spectrum, " " are fluorescence emission spectral curve；
Figure 44 is the preparation of embodiment 23 based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group function
Property double phosphine cuprous bromide cluster compound electroluminescent material be dissolved in the curve of spectrum in methylene chloride, " ■ " is UV absorption in Figure 44
The curve of spectrum, " " are fluorescence emission spectral curve；
Figure 45 is the preparation of embodiment 24 based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group function
Property double phosphine cuprous iodide cluster compound electroluminescent material be dissolved in the curve of spectrum in methylene chloride, " ■ " is UV absorption in Figure 45
The curve of spectrum, " " are fluorescence emission spectral curve；
Figure 46 is to be prepared using embodiment 22 based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The efficiency chart of the electroluminescent device of functional double phosphine stannous chloride cluster compound electroluminescent materials preparation, 1 is electric current in Figure 46
Ciency-luminance curve, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 47 is to be prepared using embodiment 23 based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The efficiency chart of the electroluminescent device of functional double phosphine cuprous bromide cluster compound electroluminescent materials preparation, 1 is electric current in Figure 47
Ciency-luminance curve, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 48 is to be prepared using embodiment 24 based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The efficiency chart of the electroluminescent device of functional double phosphine cuprous iodide cluster compound electroluminescent materials preparation, 1 is electric current in Figure 48
Ciency-luminance curve, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 49 is the preparation of embodiment 25 based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group function
Property double phosphine stannous chloride cluster compound electroluminescent material be dissolved in the curve of spectrum in methylene chloride, " ■ " is UV absorption in Figure 49
The curve of spectrum, " " are fluorescence emission spectral curve；
Figure 50 is the preparation of embodiment 26 based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group function
Property double phosphine cuprous bromide cluster compound electroluminescent material be dissolved in the curve of spectrum in methylene chloride, " ■ " is UV absorption in Figure 50
The curve of spectrum, " " are fluorescence emission spectral curve；
Figure 51 is the preparation of embodiment 27 based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group function
Property double phosphine cuprous iodide cluster compound electroluminescent material be dissolved in the curve of spectrum in methylene chloride, " ■ " is UV absorption in Figure 51
The curve of spectrum, " " are fluorescence emission spectral curve；
Figure 52 is to be prepared using embodiment 25 based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The efficiency chart of the electroluminescent device of functional double phosphine stannous chloride cluster compound electroluminescent materials preparation, 1 is electric current in Figure 52
Ciency-luminance curve, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 53 is to be prepared using embodiment 26 based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The efficiency chart of the electroluminescent device of functional double phosphine cuprous bromide cluster compound electroluminescent materials preparation, 1 is electric current in Figure 53
Ciency-luminance curve, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 54 is to be prepared using embodiment 27 based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The efficiency chart of the electroluminescent device of functional double phosphine cuprous iodide cluster compound electroluminescent materials preparation, 1 is electric current in Figure 54
Ciency-luminance curve, 2 be power efficiency-brightness curve, and 3 be external quantum efficiency-brightness curve；
Figure 55 is the double phosphine stannous chloride cluster compounds of the functionality based on dibenzothiophenes group prepared using embodiment one
The EL spectra figure of electroluminescent material preparation；
Figure 56 is the double phosphine cuprous bromide cluster compounds of the functionality based on dibenzothiophenes group prepared using embodiment two
The EL spectra figure of electroluminescent material preparation；
Figure 57 is the double phosphine cuprous iodide cluster compounds of the functionality based on dibenzothiophenes group prepared using embodiment three
The EL spectra figure of electroluminescent material preparation；
Figure 58 is to be prepared using example IV based on the functional double phosphine chlorinations of bis- carbazoles of 4,7--dibenzothiophenes group
The EL spectra figure of cuprous cluster compound electroluminescent material preparation；
Figure 59 is to be prepared using embodiment five based on the functional double phosphine bromine chlorine of bis- carbazoles of 4,7--dibenzothiophenes group
Change the EL spectra figure of cuprous cluster compound electroluminescent material preparation；
Figure 60 is to be prepared using embodiment six based on the functional double phosphine iodate of bis- carbazoles of 4,7--dibenzothiophenes group
The EL spectra figure of cuprous cluster compound electroluminescent material preparation；
Figure 61 is to be prepared using embodiment seven based on 4,7- di-t-butyl carbazole-dibenzothiophenes group functional pair
The EL spectra figure of phosphine stannous chloride cluster compound electroluminescent material preparation；
Figure 62 is to be prepared using embodiment eight based on 4,7- di-t-butyl carbazole-dibenzothiophenes group functional pair
The EL spectra figure of phosphine cuprous bromide cluster compound electroluminescent material preparation；
Figure 63 is to be prepared using embodiment nine based on 4,7- di-t-butyl carbazole-dibenzothiophenes group functional pair
The EL spectra figure of phosphine cuprous iodide cluster compound electroluminescent material preparation；
Figure 64 is to be prepared using embodiment ten based on the functional double phosphine chlorinations of 4,7- diphenylamines-dibenzothiophenes group
The EL spectra figure of cuprous cluster compound electroluminescent material preparation；
Figure 65 is to be prepared using embodiment 11 based on the functional double phosphine bromines of 4,7- diphenylamines-dibenzothiophenes group
Change the EL spectra figure of cuprous cluster compound electroluminescent material preparation；
Figure 66 is to be prepared using embodiment 12 based on the functional double phosphine iodine of 4,7- diphenylamines-dibenzothiophenes group
Change the EL spectra figure of cuprous cluster compound electroluminescent material preparation；
Figure 67 is to be prepared using embodiment 13 based on the functional double phosphine chlorine of 4,7- triphenylamine-dibenzothiophenes group
Change the EL spectra figure of cuprous cluster compound electroluminescent material preparation；
Figure 68 is to be prepared using embodiment 14 based on the functional double phosphine bromines of 4,7- triphenylamine-dibenzothiophenes group
Change the EL spectra figure of cuprous cluster compound electroluminescent material preparation；
Figure 69 is to be prepared using embodiment 15 based on the functional double phosphine iodine of 4,7- triphenylamine-dibenzothiophenes group
Change the EL spectra figure of cuprous cluster compound electroluminescent material preparation；
Figure 70 is to be prepared using embodiment 16 based on 4,7- dendroid carbazole-dibenzothiophenes group functional pair
The EL spectra figure of phosphine stannous chloride cluster compound electroluminescent material preparation；
Figure 71 is to be prepared using embodiment 17 based on 4,7- dendroid carbazole-dibenzothiophenes group functional pair
The EL spectra figure of phosphine cuprous bromide cluster compound electroluminescent material preparation；
Figure 72 is to be prepared using embodiment 18 based on 4,7- dendroid carbazole-dibenzothiophenes group functional pair
The EL spectra figure of phosphine cuprous iodide cluster compound electroluminescent material preparation；
Figure 73 is to be prepared using embodiment 19 based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group function
The EL spectra figure of the double phosphine stannous chloride cluster compound electroluminescent materials preparations of energy property；
Figure 74 is to be prepared using embodiment 20 based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group function
The EL spectra figure of the double phosphine cuprous bromide cluster compound electroluminescent materials preparations of energy property；
Figure 75 is to be prepared using embodiment 21 based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group
The EL spectra figure of functional double phosphine cuprous iodide cluster compound electroluminescent material preparations；
Figure 76 is to be prepared using embodiment 22 based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The EL spectra figure of functional double phosphine stannous chloride cluster compound electroluminescent material preparations；
Figure 77 is to be prepared using embodiment 23 based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The EL spectra figure of functional double phosphine cuprous bromide cluster compound electroluminescent material preparations；
Figure 78 is to be prepared using embodiment 24 based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The EL spectra figure of functional double phosphine cuprous iodide cluster compound electroluminescent material preparations；
Figure 79 is to be prepared using embodiment 25 based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The EL spectra figure of functional double phosphine stannous chloride cluster compound electroluminescent material preparations；
Figure 80 is to be prepared using embodiment 26 based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The EL spectra figure of functional double phosphine cuprous bromide cluster compound electroluminescent material preparations；
Figure 81 is to be prepared using embodiment 27 based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The EL spectra figure of functional double phosphine cuprous bromide cluster compound electroluminescent material preparations.
Specific embodiment
Specific embodiment 1: present embodiment is a kind of double phosphine copper clusters of the functionality based on dibenzothiophenes group
What the preparation method of electroluminescent material was specifically realized by the following steps:
Functional biphosphine ligand, cuprous halide and methylene chloride are mixed, then react 10h at being 40 DEG C~45 DEG C in temperature
~15h reuses Rotary Evaporators and is spin-dried for, obtains solid matter；It the use of the mixed liquor of methylene chloride and petroleum ether is eluent
Column chromatographic purifying is carried out, the double phosphine copper cluster electroluminescent materials of functionality based on dibenzothiophenes group are obtained；
The mass ratio of the material of the functional biphosphine ligand and cuprous halide is (0.5~3): 1；The functionality is double
The amount of the substance of Phosphine ligands and the volume ratio of methylene chloride are 1mmol:(3mL~10mL)；The functional biphosphine ligand isWherein, the Z be H, The PPh2Structure be
Specific embodiment 2: the difference of present embodiment and specific embodiment one is: the methylene chloride and
The volume ratio of methylene chloride and petroleum ether is 1:20 in the mixed liquor of petroleum ether.Other are same as the specific embodiment one.
Specific embodiment 3: the difference of present embodiment and specific embodiment one or two is: the functionality
The mass ratio of the material of biphosphine ligand and cuprous halide is (1~3): 1.Other are identical as one of specific embodiment one or two.
Specific embodiment 4: the difference of present embodiment and specific embodiment one to three is: the functionality
The mass ratio of the material of biphosphine ligand and cuprous halide is (2~3): 1.Other are identical as one of specific embodiment one to three.
Specific embodiment 5: the difference of present embodiment and specific embodiment one to four is: the functionality
The amount of the substance of biphosphine ligand and the volume ratio of methylene chloride are 1mmol:(3mL~5mL).Other with specific embodiment one to
One of four is identical.
Specific embodiment 6: the difference of present embodiment and specific embodiment one to five is: the functionality
The amount of the substance of biphosphine ligand and the volume ratio of methylene chloride are 1mmol:(5mL~10mL).Other and specific embodiment one
It is identical to one of five.
Specific embodiment 7: the difference of present embodiment and specific embodiment one to six is: the halogenation is sub-
Copper is stannous chloride, cuprous bromide or cuprous iodide.Other are identical as one of specific embodiment one to six.
Specific embodiment 8: the difference of present embodiment and specific embodiment one to seven is: by functional double phosphines
Ligand, cuprous halide and methylene chloride mixing, then 10h~13h is reacted at being 40 DEG C~45 DEG C in temperature, reuse rotary evaporation
Instrument is spin-dried for, and obtains solid matter；The use of the mixed liquor of methylene chloride and petroleum ether is that eluent carries out column chromatographic purifying, obtains base
In the double phosphine copper cluster electroluminescent materials of the functionality of dibenzothiophenes group.One of other and specific embodiment one to seven
It is identical.
Specific embodiment 9: present embodiment is a kind of double phosphine copper clusters of the functionality based on dibenzothiophenes group
Electroluminescent material is applied in electroluminescent device as emitting layer material.
Embodiment one is illustrated to embodiment 27 in conjunction with FIG. 1 to FIG. 81.
A kind of embodiment one: the double phosphine stannous chloride cluster compound electroluminescent materials of functionality based on dibenzothiophenes group
Preparation method be specifically realized by the following steps:
1mmol functionality biphosphine ligand, 1mmol cuprous halide and 5mL methylene chloride are mixed, then in the case where temperature is 45 DEG C
13h is reacted, Rotary Evaporators is reused and is spin-dried for, obtain solid matter；It the use of the mixed liquor of methylene chloride and petroleum ether is elution
Agent carries out column chromatographic purifying, obtains the double phosphine stannous chloride cluster compound electroluminescence materials of functionality based on dibenzothiophenes group
Material；
The functional biphosphine ligand isWherein, the Z is H；The cuprous halide is chlorination
It is cuprous；The volume ratio of methylene chloride and petroleum ether is 1:20 in the mixed liquor of the methylene chloride and petroleum ether.
The double phosphine stannous chloride cluster compound electroluminescence materials of functionality based on dibenzothiophenes group prepared by embodiment one
The structural formula of material are as follows:Wherein, the X is Cl；The Z is H；
The double phosphine stannous chloride clusters of the functionality based on dibenzothiophenes group prepared using Mass Spectrometer Method embodiment one are closed
Object electroluminescent material, testing result are 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 functionality based on dibenzothiophenes group prepared using embodiment one
The method for changing the electroluminescent device of cuprous cluster compound electroluminescent material preparation is as follows:
One, the glass cleaned through deionized water is put into vacuum evaporation instrument, vacuum degree is 1 × 10-6Mbar, evaporation rate are set
For 0.2nm s-1, evaporation material is tin indium oxide (ITO) on glass, with a thickness of the anode conductive layer of 100nm；
Two, hole transport layer material TAPC is deposited on hole injection layer, obtains with a thickness of 30nm hole transmission layer；
Three, barrier material mCP is deposited on the hole transport layer, obtains with a thickness of 10nm exciton barrier-layer；
Four, the double phosphine chlorinations of the functionality based on dibenzothiophenes group prepared by embodiment one are deposited on exciton barrier-layer
Cuprous cluster compound electroluminescent material, obtains with a thickness of 25nm luminescent layer；
Five, electron transport layer materials 3TPYMB is deposited, on the hole blocking layer with a thickness of 50nm electron transfer layer；
Six, electron injecting layer material LiF is deposited, on the electron transport layer with a thickness of 0.5nm electron injecting layer；
Seven, evaporation material is that metal with a thickness of the cathode conductive layer of 100nm is utilized implementation on electron injecting layer
The double phosphine stannous chloride cluster compound electroluminescent materials of functionality based on dibenzothiophenes group prepared by example one prepare 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 functionality based on dibenzothiophenes group prepared by embodiment one
UV absorption is 282nm, fluorescent emission 520nm.As can be seen from Figure 4, using the preparation of embodiment one based on dibenzothiophene
The maximum external quantum efficiency of the electroluminescent device of the double phosphine stannous chloride cluster compound electroluminescent materials preparations of the functionality of group is
9.8%, maximum current efficiency is 20.0cdA-1, power efficiency 24.1lm/W.
Embodiment two: the double phosphine cuprous bromide cluster compounds of functionality of the present embodiment preparation based on dibenzothiophenes group are electroluminescent
The method of luminescent material and the difference of embodiment one are: the functional biphosphine ligand isWherein, described
Z be H；The cuprous halide is cuprous bromide.Other are the same as example 1.
The double phosphine cuprous bromide cluster compound electroluminescence materials of functionality based on dibenzothiophenes group prepared by embodiment two
The structural formula of material are as follows:Wherein, the X is Br；The Z is H.
The double phosphine cuprous bromide clusters of the functionality based on dibenzothiophenes group prepared using Mass Spectrometer Method embodiment two are closed
Object electroluminescent material, testing result are 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 test and the difference of the application test of embodiment one are: swashing in step 4
The double phosphine cuprous bromide clusters of functionality of the preparation of emitting layer material embodiment two based on dibenzothiophenes group are deposited on sub- barrier layer
Object electroluminescent material is closed, is obtained with a thickness of 25nm luminescent layer.Other are identical as the application test of embodiment one.
As can be seen from Figure 2, the double phosphine cuprous bromide cluster compounds of the functionality based on dibenzothiophenes group prepared by embodiment two
UV absorption is 282nm, fluorescent emission 522nm.As can be seen from Figure 5, using the preparation of embodiment two based on dibenzothiophene
The maximum external quantum efficiency of the electroluminescent device of the double phosphine cuprous bromide cluster compound electroluminescent materials preparations of the functionality of group is
6.5%, maximum current efficiency is 15.2cdA-1, power efficiency 24.0lm/W.
Embodiment three: the double phosphine cuprous iodide cluster compound electricity of the functionality manufactured in the present embodiment based on dibenzothiophenes group
The method of electroluminescent material and the difference of embodiment one are: the functional biphosphine ligand isWherein, described
Z be H；The cuprous halide is cuprous iodide.Other are the same as example 1.
The double phosphine cuprous iodide cluster compound electroluminescence materials of functionality based on dibenzothiophenes group prepared by embodiment three
The structural formula of material are as follows:Wherein, the X is I；The Z is H.
The double phosphine cuprous iodide clusters of the functionality based on dibenzothiophenes group prepared using Mass Spectrometer Method embodiment three are closed
Object electroluminescent material, testing result are 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 test and the difference of the application test of embodiment one are: swashing in step 4
It is electroluminescent that the double phosphine cuprous iodide cluster compounds of the functionality based on dibenzothiophenes group prepared by embodiment three are deposited on sub- barrier layer
Luminescent material obtains with a thickness of 25nm luminescent layer.Other are identical as the application test of embodiment one.
As can be seen from Figure 3, the double phosphine cuprous iodide cluster compounds of the functionality based on dibenzothiophenes group prepared by embodiment three
UV absorption is 282nm, fluorescent emission 522nm.As can be seen from Figure 6, using the preparation of embodiment three based on dibenzothiophene
The maximum external quantum efficiency of the electroluminescent device of the double phosphine cuprous iodide cluster compound electroluminescent materials preparations of the functionality of group is
7.1%, maximum current efficiency is 15.8cdA-1, power efficiency 22.1lm/W.
Example IV: manufactured in the present embodiment based on the functional double phosphine chlorinations of bis- carbazoles of 4,7--dibenzothiophenes group
The difference of the method and embodiment one of cuprous cluster compound electroluminescent material is: the functional biphosphine ligand isWherein, the Z isThe cuprous halide is stannous chloride.Other with one phase of embodiment
Together.
Example IV preparation based on the functional double phosphine stannous chloride cluster compounds of bis- carbazoles of 4,7--dibenzothiophenes group
The structural formula of electroluminescent material are as follows:Wherein, the X is Cl；The Z is
Using the preparation of Mass Spectrometer Method example IV based on the functional double phosphine chlorine of bis- carbazoles of 4,7--dibenzothiophenes group
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 test and the difference of the application test of embodiment one are: swashing in step 4
Be deposited on sub- barrier layer example IV preparation based on the functional double phosphine stannous chlorides of bis- carbazoles of 4,7--dibenzothiophenes group
Cluster compound electroluminescent material obtains with a thickness of 25nm luminescent layer.Other are identical as the application test of embodiment one.
As can be seen from Figure 7, example IV preparation based on the functional double phosphine chlorinations of 4,7-, bis- carbazoles-dibenzothiophenes group
Cuprous cluster compound UV absorption is 282nm, fluorescent emission 520nm.As can be seen from Figure 10, using example IV preparation based on 4,
The electroluminescent cell of the functional double phosphine stannous chloride cluster compound electroluminescent material preparations 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 20.2lm/W.
Embodiment five: manufactured in the present embodiment based on the functional double phosphine brominations of bis- carbazoles of 4,7--dibenzothiophenes group
The difference of the method and embodiment one of cuprous cluster compound electroluminescent material is: the functional biphosphine ligand isWherein, the Z isThe cuprous halide is cuprous bromide.Other with one phase of embodiment
Together.
Embodiment five prepare based on the functional double phosphine cuprous bromide cluster compounds of bis- carbazoles of 4,7--dibenzothiophenes group
The structural formula of electroluminescent material are as follows:Wherein, the X is Br；The Z is
Using the preparation of Mass Spectrometer Method embodiment five based on the functional double phosphine bromines of bis- carbazoles of 4,7--dibenzothiophenes group
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 test and the difference of the application test of embodiment one are: swashing in step 4
Be deposited prepared by embodiment five on sub- barrier layer based on the functional double phosphine chlorine protobromides of bis- carbazoles of 4,7--dibenzothiophenes group
Copper cluster electroluminescent material obtains with a thickness of 25nm luminescent layer.Other are identical as the application test of embodiment one.
As it can be observed in the picture that embodiment five prepare based on the functional double phosphine brominations of 4,7-, bis- carbazoles-dibenzothiophenes group
Cuprous cluster compound UV absorption is 281nm, fluorescent emission 519nm.As can be seen from Figure 11, using the preparation of implementation five based on 4,7-
The electroluminescent device of the double phosphine cuprous bromide cluster compound electroluminescent material preparations of the functionality of two carbazoles-dibenzothiophenes group
Maximum external quantum efficiency be 8.1%, maximum current efficiency be 20.5cdA-1, power efficiency 16.3lm/W.
Embodiment six: manufactured in the present embodiment based on the functional double phosphine iodate of bis- carbazoles of 4,7--dibenzothiophenes group
The difference of the method and embodiment one of cuprous cluster compound electroluminescent material is: the functional biphosphine ligand isWherein, the Z isThe cuprous halide is cuprous iodide.Other with one phase of embodiment
Together.
Embodiment six prepare based on the functional double phosphine cuprous iodide cluster compounds of bis- carbazoles of 4,7--dibenzothiophenes group
The structural formula of electroluminescent material are as follows:Wherein, the X is I；The Z is
Using the preparation of Mass Spectrometer Method embodiment six based on the functional double phosphine iodine of bis- carbazoles of 4,7--dibenzothiophenes group
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 test and the difference of the application test of embodiment one are: swashing in step 4
Be deposited prepared by embodiment six on sub- barrier layer based on the functional double phosphine cuprous iodides of bis- carbazoles of 4,7--dibenzothiophenes group
Cluster compound electroluminescent material obtains with a thickness of 25nm luminescent layer.Other are identical as the application test of embodiment one.
As can be seen from Figure 9, embodiment six is based on the functional double phosphine cuprous iodide clusters of 4,7-, bis- carbazoles-dibenzothiophenes group
Conjunction object UV absorption is 281nm, fluorescent emission 521nm.As can be seen from Figure 12, using the preparation of embodiment six based on 4,7-, bis- click
The electroluminescent device of the functional double phosphine cuprous iodide cluster compound electroluminescent material preparations of azoles-dibenzothiophenes group is most
Big external quantum efficiency is 5.7%, and maximum current efficiency is 21.1cdA-1, power efficiency 22.4lm/W.
Embodiment seven: manufactured in the present embodiment functional double based on 4,7- di-t-butyl carbazole-dibenzothiophenes group
The difference of the method and embodiment one of phosphine stannous chloride cluster compound electroluminescent material is: the functional biphosphine ligand isWherein, the Z isThe cuprous halide is stannous chloride.Other with one phase of embodiment
Together.
Embodiment seven prepare based on the functional double phosphine stannous chlorides of 4,7- di-t-butyl carbazole-dibenzothiophenes group
The structural formula of cluster compound electroluminescent material are as follows:Wherein, the X is Cl；The Z is
Using the preparation of Mass Spectrometer Method embodiment seven based on 4,7- di-t-butyl carbazole-dibenzothiophenes group functionality
Double phosphine stannous chloride cluster compound electroluminescent materials, testing result are 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 test and the difference of the application test of embodiment one are: swashing in step 4
Be deposited prepared by embodiment seven on sub- barrier layer based on the functional double phosphine chlorine of 4,7- di-t-butyl carbazole-dibenzothiophenes group
Change cuprous cluster compound electroluminescent material, obtains with a thickness of 25nm luminescent layer.Other are identical as the application test of embodiment one.
As can be seen from Figure 13, based on the functional double phosphine stannous chloride clusters of 4,7- di-t-butyl carbazole-dibenzothiophenes group
Conjunction object UV absorption is 280nm, fluorescent emission 470nm.As can be seen from Figure 16, using the preparation of implementation seven based on the tertiary fourth of 4,7- bis-
The electroluminescent device of the functional double phosphine stannous chloride cluster compound electroluminescent material preparations of base carbazole-dibenzothiophenes group
Maximum external quantum efficiency be 6.8%, maximum current efficiency be 13.1cdA-1, power efficiency 18.7lm/W.
Embodiment eight: manufactured in the present embodiment functional double based on 4,7- di-t-butyl carbazole-dibenzothiophenes group
The difference of the method and embodiment one of phosphine cuprous bromide cluster compound electroluminescent material is: the functional biphosphine ligand isWherein, the Z isThe cuprous halide is cuprous bromide.Other with one phase of embodiment
Together.
Embodiment eight prepare based on the functional double phosphine cuprous bromides of 4,7- di-t-butyl carbazole-dibenzothiophenes group
The structural formula of cluster compound electroluminescent material are as follows:Wherein, the X is Br；The Z is
Using the preparation of Mass Spectrometer Method embodiment eight based on 4,7- di-t-butyl carbazole-dibenzothiophenes group functionality
Double phosphine cuprous bromide cluster compound electroluminescent materials, testing result are 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 test and the difference of the application test of embodiment one are: swashing in step 4
Be deposited prepared by embodiment eight on sub- barrier layer based on the functional double phosphine bromines of 4,7- di-t-butyl carbazole-dibenzothiophenes group
Change cuprous cluster compound electroluminescent material, obtains with a thickness of 25nm luminescent layer.Other are identical as the application test of embodiment one.
As can be seen from Figure 14, based on the functional double phosphine cuprous bromide clusters of 4,7- di-t-butyl carbazole-dibenzothiophenes group
Conjunction object UV absorption is 280nm, fluorescent emission 500nm.As can be seen from Figure 17, using the preparation of embodiment eight based on 4,7-, bis- uncle
The electroluminescent cell of the functional double phosphine cuprous bromide cluster compound electroluminescent material preparations 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 21.7lm/W.
Embodiment nine: manufactured in the present embodiment functional double based on 4,7- di-t-butyl carbazole-dibenzothiophenes group
The difference of the method and embodiment one of phosphine cuprous iodide cluster compound electroluminescent material is: the functional biphosphine ligand isWherein, the Z isThe cuprous halide is cuprous iodide.Other with one phase of embodiment
Together.
Embodiment nine prepare based on the functional double phosphine cuprous iodides of 4,7- di-t-butyl carbazole-dibenzothiophenes group
The structural formula of cluster compound electroluminescent material are as follows:Wherein, the X is I；The Z is
Using the preparation of Mass Spectrometer Method embodiment nine based on 4,7- di-t-butyl carbazole-dibenzothiophenes group functionality
Double phosphine cuprous iodide cluster compound electroluminescent materials, testing result are 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 test and the difference of the application test of embodiment one are: swashing in step 4
Be deposited prepared by embodiment nine on sub- barrier layer based on the functional double phosphine iodine of 4,7- di-t-butyl carbazole-dibenzothiophenes group
Change cuprous cluster compound electroluminescent material, obtains with a thickness of 25nm luminescent layer.Other are identical as the application test of embodiment one.
From figure 15, it can be known that embodiment nine prepare based on 4,7- di-t-butyl carbazole-dibenzothiophenes group functionality
Double phosphine cuprous iodide cluster compound UV absorptions are 280nm, fluorescent emission 490nm.As can be seen from Figure 18, it is prepared using embodiment nine
Based on the functional double phosphine cuprous iodide cluster compound electroluminescent material systems of 4,7- di-t-butyl 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: manufactured in the present embodiment based on the functional double phosphine chlorinations of 4,7- diphenylamines-dibenzothiophenes group
The difference of the method and embodiment one of cuprous cluster compound electroluminescent material is: the functional biphosphine ligand isWherein, the Z isThe cuprous halide is stannous chloride.Other with embodiment one
It is identical.
Embodiment ten prepare based on the functional double phosphine stannous chloride cluster compounds of 4,7- diphenylamines-dibenzothiophenes group
The structural formula of electroluminescent material are as follows:Wherein, the X is Cl；The Z is
Using the preparation of Mass Spectrometer Method embodiment ten based on the functional double phosphine chlorine of 4,7- diphenylamines-dibenzothiophenes group
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 test and the difference of the application test of embodiment one are: swashing in step 4
Be deposited prepared by embodiment ten on sub- barrier layer based on the functional double phosphine stannous chlorides of 4,7- diphenylamines-dibenzothiophenes group
Cluster compound electroluminescent material obtains with a thickness of 25nm luminescent layer.Other are identical as the application test of embodiment one.
As can be seen from Figure 19, embodiment ten prepare based on the functional double phosphine chlorine of 4,7- diphenylamines-dibenzothiophenes group
Changing cuprous cluster compound UV absorption is 280nm, fluorescent emission 470nm.As can be seen from Figure 22, using embodiment ten prepare based on
The electroluminescent of the functional double phosphine stannous chloride cluster compound electroluminescent material preparations 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 19.6lm/W.
Embodiment 11: manufactured in the present embodiment based on the functional double phosphine bromines of 4,7- diphenylamines-dibenzothiophenes group
The difference for changing the method and embodiment one of cuprous cluster compound electroluminescent material is: the functional biphosphine ligand isWherein, the Z isThe cuprous halide is cuprous bromide.Other are the same as example 1.
Prepared by embodiment 11 is closed based on the functional double phosphine cuprous bromide clusters of 4,7- diphenylamines-dibenzothiophenes group
The structural formula of object electroluminescent material are as follows:Wherein, the X is Br；The Z is
Using the preparation of Mass Spectrometer Method embodiment 11 based on the functional double phosphines of 4,7- diphenylamines-dibenzothiophenes group
Cuprous bromide cluster compound electroluminescent material, testing result are 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 test and the difference of the application test of embodiment one are: in step 4
Be deposited prepared by embodiment 11 on exciton barrier-layer based on the functional double phosphine brominations of 4,7- diphenylamines-dibenzothiophenes group
Cuprous cluster compound electroluminescent material, obtains with a thickness of 25nm luminescent layer.Other are identical as the application test of embodiment one.
As can be seen from Figure 20, embodiment 11 prepare based on the functional double phosphines of 4,7- diphenylamines-dibenzothiophenes group
Cuprous bromide cluster compound UV absorption is 280nm, fluorescent emission 505nm.As can be seen from Figure 23, it is prepared using embodiment 11
Based on the electroluminescent of the functional double phosphine cuprous bromide cluster compound electroluminescent material preparations of 4,7- diphenylamines-dibenzothiophenes group
The maximum external quantum efficiency of luminescent device is 6.8%, and maximum current efficiency is 19.8cdA-1, power efficiency 20.0lm/W.
Embodiment 12: manufactured in the present embodiment based on the functional double phosphine iodine of 4,7- diphenylamines-dibenzothiophenes group
The difference for changing the method and embodiment one of cuprous cluster compound electroluminescent material is: the functional biphosphine ligand isWherein, the Z isThe cuprous halide is cuprous iodide.Other with one phase of embodiment
Together.
Prepared by embodiment 12 is closed based on the functional double phosphine cuprous iodide clusters of 4,7- diphenylamines-dibenzothiophenes group
The structural formula of object electroluminescent material are as follows:Wherein, the X is I；The Z is
Using the preparation of Mass Spectrometer Method embodiment 12 based on the functional double phosphines of 4,7- diphenylamines-dibenzothiophenes group
Cuprous iodide cluster compound electroluminescent material, testing result are 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 test and the difference of the application test of embodiment one are: in step 4
Be deposited prepared by embodiment 12 on exciton barrier-layer based on the functional double phosphine iodate of 4,7- diphenylamines-dibenzothiophenes group
Cuprous cluster compound electroluminescent material, obtains with a thickness of 25nm luminescent layer.Other are identical as the application test of embodiment one.
As can be seen from Figure 21, embodiment 12 prepare based on the functional double phosphines of 4,7- diphenylamines-dibenzothiophenes group
Cuprous iodide cluster compound UV absorption is 280nm, fluorescent emission 490nm.As can be seen from Figure 24, it is prepared using embodiment 12
Based on the electroluminescent of the functional double phosphine cuprous iodide cluster compound electroluminescent material preparations of 4,7- diphenylamines-dibenzothiophenes group
The maximum external quantum efficiency of luminescent device is 6.4%, and maximum current efficiency is 21.1cdA-1, power efficiency 18.2lm/W.
Embodiment 13: manufactured in the present embodiment based on the functional double phosphine chlorine of 4,7- triphenylamine-dibenzothiophenes group
The difference for changing the method and embodiment one of cuprous cluster compound electroluminescent material is: the functional biphosphine ligand isWherein, the Z isThe cuprous halide is stannous chloride.Other with one phase of embodiment
Together.
Prepared by embodiment 13 is closed based on the functional double phosphine stannous chloride clusters of 4,7- triphenylamine-dibenzothiophenes group
The structural formula of object electroluminescent material are as follows:Wherein, the X is Cl；The Z is
Using the preparation of Mass Spectrometer Method embodiment 13 based on the functional double phosphines of 4,7- triphenylamine-dibenzothiophenes group
Stannous chloride cluster compound electroluminescent material, testing result are 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 test and the difference of the application test of embodiment one are: in step 4
Be deposited prepared by embodiment 13 on exciton barrier-layer based on the functional double phosphine chlorinations of 4,7- triphenylamine-dibenzothiophenes group
Cuprous cluster compound electroluminescent material, obtains with a thickness of 25nm luminescent layer.Other are identical as the application test of embodiment one.
As can be seen from Figure 25, embodiment 13 prepare based on the functional double phosphines of 4,7- triphenylamine-dibenzothiophenes group
Stannous chloride cluster compound UV absorption is 280nm, fluorescent emission 480nm.As can be seen from Figure 28, it is prepared using embodiment 13
Based on the electroluminescent of the functional double phosphine stannous chloride cluster compound electroluminescent material preparations of 4,7- triphenylamine-dibenzothiophenes group
The maximum external quantum efficiency of luminescent device is 8.1%, and maximum current efficiency is 21.1cdA-1, power efficiency 19.5lm/W.
Embodiment 14: manufactured in the present embodiment based on the functional double phosphine bromines of 4,7- triphenylamine-dibenzothiophenes group
The difference for changing the method and embodiment one of cuprous cluster compound electroluminescent material is: the functional biphosphine ligand isWherein, the Z isThe cuprous halide is cuprous bromide.Other are the same as example 1.
Prepared by embodiment 14 is closed based on the functional double phosphine stannous chloride clusters of 4,7- triphenylamine-dibenzothiophenes group
The structural formula of object electroluminescent material are as follows:Wherein, the X is Br；The Z is
Using the preparation of Mass Spectrometer Method embodiment 14 based on the functional double phosphines of 4,7- triphenylamine-dibenzothiophenes group
Cuprous bromide cluster compound electroluminescent material, testing result are 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 test and the difference of the application test of embodiment one are: in step 4
Be deposited prepared by embodiment 14 on exciton barrier-layer based on the functional double phosphine brominations of 4,7- triphenylamine-dibenzothiophenes group
Cuprous cluster compound electroluminescent material, obtains with a thickness of 25nm luminescent layer.Other are identical as the application test of embodiment one.
As can be seen from Figure 26, embodiment 14 prepare based on the functional double phosphines of 4,7- triphenylamine-dibenzothiophenes group
Cuprous bromide cluster compound UV absorption is 280nm, fluorescent emission 500nm.As can be seen from Figure 29, it is prepared using embodiment 14
Based on the electroluminescent of the functional double phosphine cuprous bromide cluster compound electroluminescent material preparations of 4,7- triphenylamine-dibenzothiophenes group
The maximum external quantum efficiency of luminescent device is 8.2%, and maximum current efficiency is 20.7cdA-1, power efficiency 21.5lm/W.
Embodiment 15: manufactured in the present embodiment based on the functional double phosphine iodine of 4,7- triphenylamine-dibenzothiophenes group
The difference for changing the method and embodiment one of cuprous cluster compound electroluminescent material is: the functional biphosphine ligand isWherein, the Z isThe cuprous halide is cuprous iodide.Other are the same as example 1.
Prepared by embodiment 15 is closed based on the functional double phosphine cuprous iodide clusters of 4,7- triphenylamine-dibenzothiophenes group
The structural formula of object electroluminescent material are as follows:Wherein, the X is I；The Z is
Using the preparation of Mass Spectrometer Method embodiment 15 based on the functional double phosphines of 4,7- triphenylamine-dibenzothiophenes group
Cuprous iodide cluster compound electroluminescent material, testing result are 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 test and the difference of the application test of embodiment one are: in step 4
Be deposited prepared by embodiment 15 on exciton barrier-layer based on the functional double phosphine iodate of 4,7- triphenylamine-dibenzothiophenes group
Cuprous cluster compound electroluminescent material, obtains with a thickness of 25nm luminescent layer.Other are identical as the application test of embodiment one.
As can be seen from Figure 27, embodiment 15 prepare based on the functional double phosphines of 4,7- triphenylamine-dibenzothiophenes group
Cuprous iodide cluster compound UV absorption is 280nm, fluorescent emission 490nm.As can be seen from Figure 30, it is prepared using embodiment 15
Based on the electroluminescent of the functional double phosphine cuprous iodide cluster compound electroluminescent material preparations of 4,7- triphenylamine-dibenzothiophenes group
The maximum external quantum efficiency of luminescent device is 7.8%, and maximum current efficiency is 21.4cdA-1, power efficiency 17.1lm/W.
Embodiment 16: manufactured in the present embodiment functional double based on 4,7- dendroid carbazole-dibenzothiophenes group
The difference of the method and embodiment one of phosphine stannous chloride cluster compound electroluminescent material is: the functional biphosphine ligand isWherein, the Z isThe cuprous halide is stannous chloride.Other with one phase of embodiment
Together.
Embodiment 16 prepare based on the functional double phosphine stannous chlorides of 4,7- dendroid carbazole-dibenzothiophenes group
The structural formula of cluster compound electroluminescent material are as follows:Wherein, the X is Cl；The Z is
Using the preparation of Mass Spectrometer Method embodiment 16 based on 4,7- dendroid carbazole-dibenzothiophenes group functionality
Double phosphine stannous chloride cluster compound electroluminescent materials, testing result are 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 test and the difference of the application test of embodiment one are: in step 4
Be deposited prepared by embodiment 16 on exciton barrier-layer based on the functional double phosphines of 4,7- dendroid carbazole-dibenzothiophenes group
Stannous chloride cluster compound electroluminescent material, obtains with a thickness of 25nm luminescent layer.Other with the application test phase of embodiment one
Together.
As can be seen from Figure 31, it is closed based on the functional double phosphine stannous chloride clusters of 4,7- dendroid carbazole-dibenzothiophenes group
Object UV absorption is 280nm, fluorescent emission 440nm.As can be seen from Figure 34,4, the 7- dendroid click prepared using embodiment 16
The electroluminescent device of the functional double phosphine stannous chloride cluster compound electroluminescent material preparations of azoles-dibenzothiophenes group is most
Big external quantum efficiency is 9.0%, and maximum current efficiency is 20.1cdA-1, power efficiency 27.0lm/W.
Embodiment 17: manufactured in the present embodiment functional double based on 4,7- dendroid carbazole-dibenzothiophenes group
The method of phosphine cuprous bromide cluster compound electroluminescent material is not both with embodiment one: the functional biphosphine ligand isWherein, the Z isThe cuprous halide is cuprous bromide.Other with one phase of embodiment
Together.
Embodiment 17 prepare based on the functional double phosphine cuprous bromides of 4,7- dendroid carbazole-dibenzothiophenes group
The structural formula of cluster compound electroluminescent material are as follows:Wherein, the X is Br；The Z is
Using the preparation of Mass Spectrometer Method embodiment 17 based on 4,7- dendroid carbazole-dibenzothiophenes group functionality
Double phosphine cuprous bromide cluster compound electroluminescent materials, testing result are 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 test is not both with the application test of embodiment one: swashing in step 4
Be deposited prepared by embodiment 17 on sub- barrier layer based on the functional double phosphine bromines of 4,7- dendroid carbazole-dibenzothiophenes group
Change cuprous cluster compound electroluminescent material, obtains with a thickness of 25nm luminescent layer.Other are identical as the application test of embodiment one.
As can be seen from Figure 32, it is closed based on the functional double phosphine cuprous bromide clusters of 4,7- dendroid carbazole-dibenzothiophenes group
Object UV absorption is 280nm, fluorescent emission 490nm.As can be seen from Figure 35, using the preparation of embodiment 17 based on 4,7- branch
The electroluminescent device of the functional double phosphine cuprous bromide cluster compound electroluminescent material preparations of shape carbazole-dibenzothiophenes group
Maximum external quantum efficiency be 7.5%, maximum current efficiency be 20.0cdA-1, power efficiency 24.7lm/W.
Embodiment 18: manufactured in the present embodiment functional double based on 4,7- dendroid carbazole-dibenzothiophenes group
The difference of the method and embodiment one of phosphine cuprous iodide cluster compound electroluminescent material is: the functional biphosphine ligand isWherein, the Z isThe cuprous halide is cuprous iodide.Other with one phase of embodiment
Together.
Embodiment 18 prepare based on the functional double phosphine cuprous iodides of 4,7- dendroid carbazole-dibenzothiophenes group
The structural formula of cluster compound electroluminescent material are as follows:Wherein, the X is I；The Z is
Using the preparation of Mass Spectrometer Method embodiment 18 based on 4,7- dendroid carbazole-dibenzothiophenes group functionality
Double phosphine cuprous iodide cluster compound electroluminescent materials, testing result are 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 test and the difference of the application test of embodiment one are: in step 4
Be deposited prepared by embodiment 18 on exciton barrier-layer based on the functional double phosphines of 4,7- dendroid carbazole-dibenzothiophenes group
Cuprous iodide cluster compound electroluminescent material, obtains with a thickness of 25nm luminescent layer.Other with the application test phase of embodiment one
Together.
As can be seen from Figure 33, embodiment 18 prepare based on 4,7- dendroid carbazole-dibenzothiophenes group functionality
Double phosphine cuprous iodide cluster compound UV absorptions are 280nm, fluorescent emission 490nm.As can be seen from Figure 36, it is made using embodiment 18
It is standby based on the functional double phosphine cuprous iodide cluster compound electroluminescent material systems of 4,7- dendroid 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: manufactured in the present embodiment based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group function
The difference of the method and embodiment one of the double phosphine stannous chloride cluster compound electroluminescent materials of energy property is: the double phosphines of the functionality
Ligand isWherein, the Z isThe cuprous halide is stannous chloride.Other with reality
It is identical to apply example one.
Embodiment 19 prepare based on the functional double phosphine chlorine of 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group
Change the structural formula of cuprous cluster compound electroluminescent material are as follows:Wherein, the X is Cl；The Z is
Using the preparation of Mass Spectrometer Method embodiment 19 based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group
Functional double phosphine stannous chloride cluster compound electroluminescent materials, testing result are 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 test and the difference of the application test of embodiment one are: in step 4
On exciton barrier-layer be deposited embodiment 19 prepare based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group function
Property double phosphine stannous chloride cluster compound electroluminescent material, obtain with a thickness of 25nm luminescent layer.Other applications with embodiment one
It tests identical.
As can be seen from Figure 37, embodiment 19 prepare based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group
Functional double phosphine stannous chloride cluster compound UV absorptions are 280nm, fluorescent emission 460nm.As can be seen from Figure 40, embodiment is utilized
19 preparations based on the functional double phosphine stannous chloride cluster compounds electricity of 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group
The maximum external quantum efficiency of the electroluminescent device of electroluminescent material preparation is 7.8%, and maximum current efficiency is 20.2cdA-1,
Power efficiency is 27.0lm/W.
Embodiment 20: manufactured in the present embodiment based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group function
The difference of the method and embodiment one of the double phosphine cuprous bromide cluster compound electroluminescent materials of energy property is: the double phosphines of the functionality
Ligand isWherein, the Z isThe cuprous halide is cuprous bromide.Other with
Embodiment one is identical.
Embodiment 20 prepare based on the functional double phosphine bromines of 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group
Change the structural formula of cuprous cluster compound electroluminescent material are as follows:Wherein, the X is Br；The Z is
Using the preparation of Mass Spectrometer Method embodiment 20 based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group
Functional double phosphine cuprous bromide cluster compound electroluminescent materials, testing result are 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 test and the difference of the application test of embodiment one are: in step 4
On exciton barrier-layer be deposited embodiment 20 prepare based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group function
Property double phosphine cuprous bromide cluster compound electroluminescent material, obtain with a thickness of 25nm luminescent layer.Other applications with embodiment one
It tests identical.
As can be seen from Figure 38, based on the functional double phosphine protobromides of 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group
Copper cluster UV absorption is 280nm, fluorescent emission 460nm.As can be seen from Figure 41, with the preparation of embodiment 20 based on 4,7-
The electricity of the functional double phosphine cuprous bromide cluster compound electroluminescent material preparations 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 27.7lm/
W。
Embodiment 21: manufactured in the present embodiment based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group
The difference of the method and embodiment one of functional double phosphine cuprous iodide cluster compound electroluminescent materials is: the functionality is double
Phosphine ligands areWherein, the Z isThe cuprous halide is cuprous iodide.Other with
Embodiment one is identical.
Embodiment 21 prepare based on the functional double phosphines of 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group
The structural formula of cuprous iodide cluster compound electroluminescent material are as follows:Wherein, the X is I；The Z is
Using the preparation of Mass Spectrometer Method embodiment 21 based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group
The double phosphine cuprous iodide cluster compound electroluminescent materials of functionality, 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 test and the difference of the application test of embodiment one are: in step 4
On exciton barrier-layer be deposited embodiment 21 prepare based on 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group
Functional double phosphine cuprous iodide cluster compound electroluminescent materials, obtain with a thickness of 25nm luminescent layer.Other with embodiment one
Application test is identical.
As can be seen from Figure 39, sub- based on the functional double phosphine iodate of 4,7- dendroid tert-butyl carbazole-dibenzothiophenes group
Copper cluster UV absorption is 280nm, fluorescent emission 495nm.As can be seen from Figure 42, using embodiment 21 prepare based on
The functional double phosphine cuprous iodide cluster compound electroluminescent material preparations of 4,7- dendroid 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: manufactured in the present embodiment based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The difference of the method and embodiment one of functional double phosphine stannous chloride cluster compound electroluminescent materials is: the functionality is double
Phosphine ligands areWherein, the Z isThe cuprous halide is stannous chloride.Other with
Embodiment one is identical.
Embodiment 22 prepare based on the functional double phosphines of 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The structural formula of stannous chloride cluster compound electroluminescent material are as follows:Wherein, the X is Cl；The Z is
Using the preparation of Mass Spectrometer Method embodiment 22 based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The double phosphine stannous chloride cluster compound electroluminescent materials of functionality, 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 test and the difference of the application test of embodiment one are: in step 4
On exciton barrier-layer be deposited embodiment 22 prepare based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
Functional double phosphine stannous chloride cluster compound electroluminescent materials, obtain with a thickness of 25nm luminescent layer.Other with embodiment one
Application test is identical.
As can be seen from Figure 43, embodiment 22 prepare based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The double phosphine stannous chloride cluster compound electroluminescent material UV absorptions of functionality be 280nm, fluorescent emission 470nm.From Figure 46
It is found that being prepared using embodiment 22 functional double based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The maximum external quantum efficiency of the electroluminescent device of phosphine stannous chloride cluster compound electroluminescent material preparation is 8.3%, maximum electricity
Stream efficiency is 20.6cdA-1, power efficiency 27.7lm/W.
Embodiment 23: manufactured in the present embodiment based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The difference of the method and embodiment one of functional double phosphine cuprous bromide cluster compound electroluminescent materials is: the functionality is double
Phosphine ligands areWherein, the Z isThe cuprous halide is cuprous bromide.Other with
Embodiment one is identical.
Embodiment 23 prepare based on the functional double phosphines of 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The structural formula of cuprous bromide cluster compound electroluminescent material are as follows:Wherein, the X is Br；The Z is
Using the preparation of Mass Spectrometer Method embodiment 23 based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The double phosphine cuprous bromide cluster compound electroluminescent materials of functionality, 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 test and the difference of the application test of embodiment one are: in step 4
On exciton barrier-layer be deposited embodiment 23 prepare based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
Functional double phosphine cuprous bromide cluster compound electroluminescent materials, obtain with a thickness of 25nm luminescent layer.Other with embodiment one
Application test is identical.
As can be seen from Figure 44, embodiment 23 prepare based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The double phosphine cuprous bromide cluster compound electroluminescent material UV absorptions of functionality be 280nm, fluorescent emission 500nm.From Figure 47
It is found that being prepared using embodiment 23 functional double based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The maximum external quantum efficiency of the electroluminescent device of phosphine cuprous bromide cluster compound electroluminescent material preparation is 7.9%, maximum electricity
Stream efficiency is 20.8cdA-1, power efficiency 22.3lm/W.
Embodiment 24: manufactured in the present embodiment based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The difference of the method and embodiment one of functional double phosphine cuprous iodide cluster compound electroluminescent materials is: the functionality is double
Phosphine ligands areWherein, the Z isThe cuprous halide is cuprous iodide.Other with
Embodiment one is identical.
Embodiment 24 prepare based on the functional double phosphines of 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The structural formula of cuprous iodide cluster compound electroluminescent material are as follows:Wherein, the X is I；The Z is
Using the preparation of Mass Spectrometer Method embodiment 24 based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The double phosphine cuprous iodide cluster compound electroluminescent materials of functionality, 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 test and the difference of the application test of embodiment one are: in step 4
On exciton barrier-layer be deposited embodiment 24 prepare based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
Functional double phosphine cuprous iodide cluster compound electroluminescent materials, obtain with a thickness of 25nm luminescent layer.Other with embodiment one
Application test is identical.
As can be seen from Figure 45, embodiment 24 prepare based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The double phosphine cuprous iodide cluster compound electroluminescent material UV absorptions of functionality be 282nm, fluorescent emission 490nm.From Figure 48
It is found that being prepared using embodiment 24 functional double based on 4,7- dendroid carbazole diphenylamines-dibenzothiophenes group
The maximum external quantum efficiency of the electroluminescent device of phosphine cuprous iodide cluster compound electroluminescent material preparation is 8%, maximum current
Efficiency is 21.4cdA-1, power efficiency 26.4lm/W.
Embodiment 25: manufactured in the present embodiment based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The difference of the method and embodiment one of functional double phosphine stannous chloride cluster compound electroluminescent materials is: the functionality is double
Phosphine ligands areWherein, the Z isThe cuprous halide is stannous chloride.Other with
Embodiment one is identical.
Embodiment 25 prepare based on the functional double phosphines of 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The structural formula of stannous chloride cluster compound electroluminescent material are as follows:Wherein, the X is Cl；The Z is
Using the preparation of Mass Spectrometer Method embodiment 25 based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The double phosphine stannous chloride cluster compound electroluminescent materials of functionality, 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 test and the difference of the application test of embodiment one are: in step 4
On exciton barrier-layer be deposited embodiment 25 prepare based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
Functional double phosphine stannous chloride cluster compound electroluminescent materials, obtain with a thickness of 25nm luminescent layer.Other with embodiment one
Application test is identical.
As can be seen from Figure 49, embodiment 25 prepare based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The double phosphine stannous chloride cluster compound electroluminescent material UV absorptions of functionality be 280nm, fluorescent emission 465nm.From Figure 52
It is found that being prepared using embodiment 25 functional double based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The maximum external quantum efficiency of the electroluminescent device of phosphine stannous chloride cluster compound electroluminescent material preparation is 7.8%, maximum electricity
Stream efficiency is 20.1cdA-1, power efficiency 20.0lm/W.
Embodiment 26: manufactured in the present embodiment based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The difference of the method and embodiment one of functional double phosphine cuprous bromide cluster compound electroluminescent materials is: the functionality is double
Phosphine ligands areWherein, the Z isThe cuprous halide is cuprous bromide.Other are
It is the same as example 1.
Embodiment 26 prepare based on the functional double phosphines of 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The structural formula of cuprous bromide cluster compound electroluminescent material are as follows:Wherein, the X is Br；The Z is
Using the preparation of Mass Spectrometer Method embodiment 26 based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The double phosphine cuprous bromide cluster compound electroluminescent materials of functionality, 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 test and the difference of the application test of embodiment one are: in step 4
On exciton barrier-layer be deposited embodiment 26 prepare based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
Functional double phosphine cuprous bromide cluster compound electroluminescent materials, obtain with a thickness of 25nm luminescent layer.Other with embodiment one
Application test is identical.
As can be seen from Figure 50, embodiment 26 prepare based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The double phosphine cuprous bromide cluster compound electroluminescent material UV absorptions of functionality be 280nm, fluorescent emission 505nm.From Figure 53
It is found that being prepared using embodiment 26 functional double based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The maximum external quantum efficiency of the electroluminescent device of phosphine cuprous bromide cluster compound electroluminescent material preparation is 7.5%, maximum electricity
Stream efficiency is 20.0cdA-1, power efficiency 25.2lm/W.
Embodiment 27: manufactured in the present embodiment based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The difference of the method and embodiment one of functional double phosphine cuprous iodide cluster compound electroluminescent materials is: the functionality is double
Phosphine ligands areWherein, the Z isThe cuprous halide is cuprous iodide.Other with
Embodiment one is identical.
Embodiment 27 prepare based on the functional double phosphines of 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The structural formula of cuprous iodide cluster compound electroluminescent material are as follows:Wherein, the X is I；The Z is
Using the preparation of Mass Spectrometer Method embodiment 27 based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The double phosphine cuprous iodide cluster compound electroluminescent materials of functionality, 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 test and the difference of the application test of embodiment one are: in step 4
On exciton barrier-layer be deposited embodiment 27 prepare based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
Functional double phosphine cuprous iodide cluster compound electroluminescent materials, obtain with a thickness of 25nm luminescent layer.Other with embodiment one
Application test is identical.
As we know from Figure 51, embodiment 27 prepare based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The double phosphine cuprous iodide cluster compound electroluminescent material UV absorptions of functionality be 282nm, fluorescent emission 490nm.From Figure 54
It is found that being prepared using embodiment 27 functional double based on 4,7- dendroid carbazole triphenylamine-dibenzothiophenes group
The maximum external quantum efficiency of the electroluminescent device of phosphine cuprous iodide cluster compound electroluminescent material preparation is 8%, maximum current
Efficiency is 20.7cdA-1, power efficiency 24.8lm/W.
From Figure 55,56,57 it is found that electroluminescent peak value is respectively 505nm, 510nm, 515nm；It can from Figure 58,59,60
Know, electroluminescent peak value is respectively 505nm, 509nm, 500nm；From Figure 61,62,63 it is found that electroluminescent peak value is respectively
505nm,510nm,515nm；From Figure 64,65,66 it is found that electroluminescent peak value is respectively 550nm, 570nm, 520nm；From figure
67,68,69 it is found that electroluminescent peak value is respectively 510nm, 509nm, 515nm；From Figure 70,71,72 it is found that electroluminescent peak
Value is respectively 520nm, 520nm, 522nm；From Figure 73,74,75 it is found that electroluminescent peak value be respectively 560m, 580nm,
540nm；From Figure 76,77,78 it is found that electroluminescent peak value is respectively 515nm, 510nm, 515nm；From Figure 79,80,81 it is found that
Electroluminescent peak value is respectively 550nm, 540nm, 520nm.
Claims (9)
1. a kind of double phosphine copper cluster electroluminescent materials of functionality based on dibenzothiophenes group, it is characterised in that Yi Zhongji
In the structural formula of the double phosphine copper cluster electroluminescent materials of the functionality of dibenzothiophenes group are as follows:
Wherein, the X is Cl, Br or I；The Z be H, The PPh2Structure be
2. the double phosphine copper cluster electroluminescent materials of a kind of functionality based on dibenzothiophenes group as described in claim 1
Preparation method, it is characterised in that a kind of double phosphine copper cluster electroluminescent materials of functionality based on dibenzothiophenes group
What preparation method was specifically realized by the following steps:
By functional biphosphine ligand, cuprous halide and methylene chloride mix, then temperature be 40 DEG C~45 DEG C at react 10h~
15h reuses Rotary Evaporators and is spin-dried for, obtains solid matter；Using the mixed liquor of methylene chloride and petroleum ether be eluent into
Row column chromatographic purifying obtains the double phosphine copper cluster electroluminescent materials of functionality based on dibenzothiophenes group；
The mass ratio of the material of the functional biphosphine ligand and cuprous halide is (0.5~3): 1；
The amount of the substance of the functional biphosphine ligand and the volume ratio of methylene chloride are 1mmol:(3mL~10mL)；
The functional biphosphine ligand isWherein, the Z be H, The PPh2Structure be
3. the double phosphine copper cluster electroluminescence materials of a kind of functionality based on dibenzothiophenes group according to claim 2
The preparation method of material, it is characterised in that the volume of methylene chloride and petroleum ether in the mixed liquor of the methylene chloride and petroleum ether
Than for 1:20.
4. the double phosphine copper cluster electroluminescence materials of a kind of functionality based on dibenzothiophenes group according to claim 2
The preparation method of material, it is characterised in that the mass ratio of the material of the functional biphosphine ligand and cuprous halide is (1~3): 1.
5. the double phosphine copper cluster electroluminescence materials of a kind of functionality based on dibenzothiophenes group according to claim 2
The preparation method of material, it is characterised in that the mass ratio of the material of the functional biphosphine ligand and cuprous halide is (2~3): 1.
6. the double phosphine copper cluster electroluminescence materials of a kind of functionality based on dibenzothiophenes group according to claim 2
The preparation method of material, it is characterised in that the amount of substance and the volume ratio of methylene chloride of the functional biphosphine ligand be
1mmol:(3mL~5mL).
7. the double phosphine copper cluster electroluminescence materials of a kind of functionality based on dibenzothiophenes group according to claim 2
The preparation method of material, it is characterised in that the amount of substance and the volume ratio of methylene chloride of the functional biphosphine ligand be
1mmol:(5mL~10mL).
8. the double phosphine copper cluster electroluminescence materials of a kind of functionality based on dibenzothiophenes group according to claim 2
The preparation method of material, it is characterised in that by functional biphosphine ligand, cuprous halide and methylene chloride mix, then temperature be 40 DEG C
10h~13h is reacted at~45 DEG C, is reused Rotary Evaporators and is spin-dried for, obtains solid matter；Use methylene chloride and petroleum ether
Mixed liquor is that eluent carries out column chromatographic purifying, obtains the electroluminescent hair of the double phosphine copper clusters of functionality based on dibenzothiophenes group
Luminescent material.
9. the double phosphine copper cluster electroluminescent materials of a kind of functionality based on dibenzothiophenes group as described in claim 1
Application, it is characterised in that a kind of double phosphine copper cluster electroluminescent materials of functionality based on dibenzothiophenes group are as hair
Photosphere material is applied in electroluminescent device.
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