CN106831829B - A kind of double phosphine copper cluster electroluminescent materials of functionality based on dibenzofurans group and preparation method and application - Google Patents

A kind of double phosphine copper cluster electroluminescent materials of functionality based on dibenzofurans group and preparation method and application Download PDF

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CN106831829B
CN106831829B CN201710081889.4A CN201710081889A CN106831829B CN 106831829 B CN106831829 B CN 106831829B CN 201710081889 A CN201710081889 A CN 201710081889A CN 106831829 B CN106831829 B CN 106831829B
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dibenzofurans group
double phosphine
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CN106831829A (en
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许辉
谢明辰
韩春苗
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Heilongjiang University
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    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
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    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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    • C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
    • C07F9/65517—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen 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
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    • 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
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    • 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
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Abstract

A kind of double phosphine copper cluster electroluminescent materials of functionality and preparation method and application based on dibenzofurans 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 dibenzofurans 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 dibenzofurans 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 dibenzofurans group.

Description

A kind of double phosphine copper cluster electroluminescence materials of functionality based on dibenzofurans group Material and preparation method and application
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 dibenzofurans 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 dibenzofurans 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 dibenzofurans 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 dibenzofurans group have The luminous characteristics such as mechanoluminescence, luminescence generated by light, electroluminescent, the prepared by the method function based on dibenzofurans group Property double phosphine copper cluster electroluminescent material preparation luminescent device, current efficiency maximum value is 21.5cdA-1, outer quantum Maximum efficiency is 9.1%, and power efficiency maximum value is 27.5lm/W；
Three, the double phosphine copper cluster electroluminescent materials of the functionality prepared by the present invention based on dibenzofurans 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 dibenzofurans 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 dibenzofurans 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 dibenzofurans 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 dibenzofurans 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 dibenzofurans 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 dibenzofurans 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 dibenzofurans 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 dibenzofurans 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 dibenzofurans 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 dibenzofurans 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--dibenzofurans 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--dibenzofurans 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--dibenzofurans 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--dibenzofurans 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--dibenzofurans 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--dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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-dibenzofurans 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 dibenzofurans group prepared using embodiment one The electrochromism figure of the electroluminescent device of electroluminescent material preparation；
Figure 56 is the double phosphine cuprous bromide cluster compounds of the functionality based on dibenzofurans group prepared using embodiment two The electrochromism figure of the electroluminescent device of electroluminescent material preparation；
Figure 57 is the double phosphine cuprous iodide cluster compounds of the functionality based on dibenzofurans group prepared using embodiment three The electrochromism figure of the electroluminescent device 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--dibenzofurans group The electrochromism figure of the electroluminescent device 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--dibenzofurans group Change the electrochromism figure of the electroluminescent device 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--dibenzofurans group The electrochromism figure of the electroluminescent device of cuprous cluster compound electroluminescent material preparation；
Figure 61 is to be prepared using embodiment seven based on 4,7- di-t-butyl carbazole-dibenzofurans group functional pair The electrochromism figure of the electroluminescent device 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-dibenzofurans group functional pair The electrochromism figure of the electroluminescent device 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-dibenzofurans group functional pair The electrochromism figure of the electroluminescent device 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-dibenzofurans group The electrochromism figure of the electroluminescent device 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-dibenzofurans group Change the electrochromism figure of the electroluminescent device 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-dibenzofurans group Change the electrochromism figure of the electroluminescent device 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-dibenzofurans group Change the electrochromism figure of the electroluminescent device 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-dibenzofurans group Change the electrochromism figure of the electroluminescent device 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-dibenzofurans group Change the electrochromism figure of the electroluminescent device of cuprous cluster compound electroluminescent material preparation；
Figure 70 is to be prepared using embodiment 16 based on 4,7- dendroid carbazole-dibenzofurans group functional pair The electrochromism figure of the electroluminescent device of phosphine stannous chloride cluster compound electroluminescent material preparation；
Figure 71 is to be prepared using embodiment 17 based on 4,7- dendroid carbazole-dibenzofurans group functional pair The electrochromism figure of the electroluminescent device of phosphine cuprous bromide cluster compound electroluminescent material preparation；
Figure 72 is to be prepared using embodiment 18 based on 4,7- dendroid carbazole-dibenzofurans group functional pair The electrochromism figure of the electroluminescent device 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-dibenzofurans group function The electrochromism figure of the electroluminescent device 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-dibenzofurans group function The electrochromism figure of the electroluminescent device 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-dibenzofurans group The electrochromism figure of the electroluminescent device 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-dibenzofurans group The electrochromism figure of the electroluminescent device 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-dibenzofurans group The electrochromism figure of the electroluminescent device 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-dibenzofurans group The electrochromism figure of the electroluminescent device 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-dibenzofurans group The electrochromism figure of the electroluminescent device 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-dibenzofurans group The electrochromism figure of the electroluminescent device 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-dibenzofurans group The electrochromism figure of the electroluminescent device 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 dibenzofurans 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 dibenzofurans group are obtained；
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 PPh2's Structure isOther are same as the specific embodiment one.
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 the same as one or two specific embodiments.
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 five 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 dibenzofurans 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 dibenzofurans group Electroluminescent material is applied in electroluminescent device as emitting layer material.
Beneficial effects of the present invention are verified using following embodiment:
In conjunction with 1 specific illustrative embodiment one of FIG. 1 to FIG. 8 to embodiment 27:
A kind of embodiment one: the double phosphine stannous chloride cluster compound electroluminescent materials of functionality based on dibenzofurans 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 chromatography and is purified, and obtains the double phosphine stannous chloride cluster compound electroluminescent of functionality based on dibenzofurans group Material；
The functional biphosphine ligand isWherein, the Z is H；
The cuprous halide is stannous chloride；
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 dibenzofurans 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 dibenzofurans group prepared using Mass Spectrometer Method embodiment one are closed Object electroluminescent material, testing result are as follows: Exact mass:1463.89；M/z:1467.88 (100.0%)；Elemental Analysis for C72H52Cl4Cu4O2P4:C,58.87；H,3.57；O,2.18.
The application test of embodiment one: the double phosphine chlorine of the functionality based on dibenzofurans 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 dibenzofurans 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 dibenzofurans 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 dibenzofurans group prepared by embodiment one UV absorption is 281nm, fluorescent emission 510nm.As can be seen from Figure 4, using the preparation of embodiment one based on dibenzofuran group 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 1.1%, maximum current efficiency is 5.6cdA-1, power efficiency 9.3lm/W.
Embodiment two: the double phosphine cuprous bromide cluster compounds of functionality of the present embodiment preparation based on dibenzofurans 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 dibenzofurans 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 dibenzofurans group prepared using Mass Spectrometer Method embodiment two are closed Object electroluminescent material, testing result are as follows: Exact mass:1639.38；M/z:1645.68 (100.0%)；Elemental Analysis for C72H52Br4Cu4O2P4:C,52.51；H,3.18；O,1.94.
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 dibenzofurans 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 dibenzofurans group prepared by embodiment two UV absorption is 281nm, fluorescent emission 500nm.As can be seen from Figure 5, using the preparation of embodiment two based on dibenzofuran group 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 2.1%, maximum current efficiency is 8.3cdA-1, power efficiency 8.3lm/W.
Embodiment three: the double phosphine cuprous iodide cluster compound electricity of the functionality manufactured in the present embodiment based on dibenzofurans group The method of electroluminescent material and the difference of embodiment one are: the functional biphosphine ligand isWherein, institute The Z stated is 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 dibenzofurans 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 dibenzofurans group prepared using Mass Spectrometer Method embodiment three are closed Object electroluminescent material, testing result are as follows: Exact mass:1831.63；M/z:1833.63 (100.0%)；Elemental Analysis for C72H52I4Cu4O2P4:C,47.13；H,2.86；O,1.74.
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 dibenzofurans 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 dibenzofurans group prepared by embodiment three UV absorption is 280nm, fluorescent emission 480nm.As can be seen from Figure 6, using the preparation of embodiment three based on dibenzofuran group 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 3.1%, maximum current efficiency is 9.4cdA-1, power efficiency 8.2lm/W.
Example IV: manufactured in the present embodiment based on the functional double phosphine chlorinations of bis- carbazoles of 4,7--dibenzofurans 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 are the same as example 1.
Example IV preparation based on the functional double phosphine stannous chloride cluster compounds of bis- carbazoles of 4,7--dibenzofurans 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--dibenzofurans group Change cuprous cluster compound electroluminescent material, testing result is as follows: Exact Mass:2124.12；m/z:2129.12 (100.0%)；Elemental Analysis for C120H80Cl4Cu4N4O2P4:C,67.67；H,3.79；O,1.50.
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--dibenzofurans 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-dibenzofurans group Cuprous cluster compound UV absorption is 282nm, fluorescent emission 490nm.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--dibenzofurans group The maximum external quantum efficiency of part is 7.6%, and maximum current efficiency is 21.2cdA-1, power efficiency 21.4lm/W.
Embodiment five: manufactured in the present embodiment based on the functional double phosphine brominations of bis- carbazoles of 4,7--dibenzofurans 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 are the same as example 1.
Embodiment five prepare based on the functional double phosphine cuprous bromide cluster compounds of bis- carbazoles of 4,7--dibenzofurans 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--dibenzofurans group Change cuprous cluster compound electroluminescent material, testing result is as follows: Exact Mass:2299.91；m/z:2306.91 (100.0%)；Elemental Analysis:C, 62.46；H,3.49；O,1.39.
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 cuprous bromides of bis- carbazoles of 4,7--dibenzofurans group Cluster compound 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-dibenzofurans group Cuprous cluster compound UV absorption is 281nm, fluorescent emission 500nm.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-dibenzofurans group Maximum external quantum efficiency be 7.4%, maximum current efficiency be 21.4cdA-1, power efficiency 20.2lm/W.
Embodiment six: manufactured in the present embodiment based on the functional double phosphine iodate of bis- carbazoles of 4,7--dibenzofurans 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 are the same as example 1.
Embodiment six prepare based on the functional double phosphine cuprous iodide cluster compounds of bis- carbazoles of 4,7--dibenzofurans 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--dibenzofurans group Change cuprous cluster compound electroluminescent material, testing result is as follows: Exact Mass:2491.86；m/z:2494.86 (100.0%)；Elemental Analysis for C120H80I4Cu4N4O2P4:C,57.75；H,3.23；O,1.28.
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--dibenzofurans 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-dibenzofurans group Conjunction object UV absorption is 282nm, fluorescent emission 480nm.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-dibenzofurans group is most Big external quantum efficiency is 8.5%, and maximum current efficiency is 21.1cdA-1, power efficiency 27.5lm/W.
Embodiment seven: manufactured in the present embodiment functional double based on 4,7- di-t-butyl carbazole-dibenzofurans 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 are the same as example 1.
Embodiment seven prepare based on the functional double phosphine stannous chlorides of 4,7- di-t-butyl carbazole-dibenzofurans 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-dibenzofurans group functionality Double phosphine stannous chloride cluster compound electroluminescent materials, testing result are as follows: Exace mass:2572.62；m/z:2577.62 (100.0%)；Elemental Analysis for C152H144Cl4Cu4N4O2P4:C,70.80；H,5.63；O,1.24.
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-dibenzofurans 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, embodiment seven prepare based on 4,7- di-t-butyl carbazole-dibenzofurans group functionality Double phosphine stannous chloride cluster compound UV absorptions are 281nm, fluorescent emission 480nm.As can be seen from Figure 16, it is prepared using implementation seven Based on the functional double phosphine stannous chloride cluster compound electroluminescent material preparations of 4,7- di-t-butyl carbazole-dibenzofurans group Electroluminescent device maximum external quantum efficiency be 8.3%, maximum current efficiency be 19.1cdA-1, power efficiency is 27.5lm/W。
Embodiment eight: manufactured in the present embodiment functional double based on 4,7- di-t-butyl carbazole-dibenzofurans 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 are the same as example 1.
Embodiment eight prepare based on the functional double phosphine cuprous bromides of 4,7- di-t-butyl carbazole-dibenzofurans 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-dibenzofurans group functionality Double phosphine cuprous bromide cluster compound electroluminescent materials, testing result are as follows: Exace mass:2748.42；m/z:2755.41 (100.0%)；Elemental Analysis for C152H144Br4Cu4N4O2P4:C,66.23；H,5.27；O,1.16.
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-dibenzofurans 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, embodiment eight prepare based on 4,7- di-t-butyl carbazole-dibenzofurans group functionality Double phosphine cuprous bromide cluster compound UV absorptions are 281nm, fluorescent emission 500nm.As can be seen from Figure 17, it is prepared using embodiment eight Based on the functional double phosphine cuprous bromide cluster compound electroluminescent material systems of 4,7- di-t-butyl carbazole-dibenzofurans group The maximum external quantum efficiency of standby electroluminescent device is 8.1%, and maximum current efficiency is 21.1cdA-1, power efficiency is 22.1lm/W。
Embodiment nine: manufactured in the present embodiment functional double based on 4,7- di-t-butyl carbazole-dibenzofurans 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 are the same as example 1.
Embodiment nine prepare based on the functional double phosphine cuprous iodides of 4,7- di-t-butyl carbazole-dibenzofurans 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-dibenzofurans group functionality Double phosphine cuprous iodide cluster compound electroluminescent materials, testing result are as follows: Exace mass:2940.36；m/z:2943.36 (100.0%)；Elemental Analysis for C152H144I4Cu4N4O2P4:C,62.00；H,4.93；O,1.09.
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-dibenzofurans 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-dibenzofurans group functionality Double phosphine cuprous iodide cluster compound UV absorptions are 280nm, fluorescent emission 505nm.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-dibenzofurans group The maximum external quantum efficiency of standby electroluminescent device is 7.5%, and maximum current efficiency is 20.1cdA-1, power efficiency is 17.5lm/W。
Embodiment ten: manufactured in the present embodiment based on the functional double phosphine chlorinations of 4,7- diphenylamines-dibenzofurans 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 are the same as example 1.
Embodiment ten prepare based on the functional double phosphine stannous chloride cluster compounds of 4,7- diphenylamines-dibenzofurans 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-dibenzofurans group Change cuprous cluster compound electroluminescent material, testing result is as follows:
Exact Mass:2132.18；M/z:2137.18 (100.0%)；Elemental Analysis for C120H88Cl4Cu4N4O2P4:C,67.42；H,4.15；O,1.50.
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-dibenzofurans 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-dibenzofurans group Changing cuprous cluster compound UV absorption is 281nm, fluorescent emission 480nm.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-dibenzofurans group The maximum external quantum efficiency of device is 7.6%, and maximum current efficiency is 20.1cdA-1, power efficiency 22.5lm/W.
Embodiment 11: manufactured in the present embodiment based on the functional double phosphine bromines of 4,7- diphenylamines-dibenzofurans 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-dibenzofurans 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-dibenzofurans group Cuprous bromide cluster compound electroluminescent material, testing result are as follows: Exact Mass:2307.98；m/z:2314.97 (100.0%)；Elemental Analysis for C120H88Br4Cu4N4O2P4:C,62.24；H,3.83；O,1.38.
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-dibenzofurans 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-dibenzofurans group Cuprous bromide cluster compound UV absorption is 281nm, fluorescent emission 500nm.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-dibenzofurans group The maximum external quantum efficiency of luminescent device is 5.5%, and maximum current efficiency is 20.0cdA-1, power efficiency 16.2lm/W.
Embodiment 12: manufactured in the present embodiment based on the functional double phosphine iodine of 4,7- diphenylamines-dibenzofurans 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 12 is closed based on the functional double phosphine cuprous iodide clusters of 4,7- diphenylamines-dibenzofurans 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-dibenzofurans group Cuprous iodide cluster compound electroluminescent material, testing result are as follows: Exact Mass:2499.92；m/z:2502.92 (100.0%)；Elemental Analysis for C120H88I4Cu4N4O2P4:C,57.57；H,3.54；O,1.28.
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-dibenzofurans 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-dibenzofurans group Cuprous iodide cluster compound UV absorption is 280nm, fluorescent emission 500nm.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-dibenzofurans group The maximum external quantum efficiency of luminescent device is 8.1%, and maximum current efficiency is 21.5cdA-1, power efficiency 18.5lm/W.
Embodiment 13: manufactured in the present embodiment based on the functional double phosphine chlorine of 4,7- triphenylamine-dibenzofurans 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 are the same as example 1.
Prepared by embodiment 13 is closed based on the functional double phosphine stannous chloride clusters of 4,7- triphenylamine-dibenzofurans 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-dibenzofurans group Stannous chloride cluster compound electroluminescent material, testing result are as follows: Exact Mass:2436.30；m/z:2441.30 (100.0%)；Elemental Analysis for C144H104Cl4Cu4N4O2P4:C,70.82；H,4.29；O,1.31.
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-dibenzofurans 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-dibenzofurans group Stannous chloride cluster compound UV absorption is 281nm, 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-dibenzofurans group The maximum external quantum efficiency of luminescent device is 7.5%, and maximum current efficiency is 20.7cdA-1, power efficiency 25.0lm/W.
Embodiment 14: manufactured in the present embodiment based on the functional double phosphine bromines of 4,7- triphenylamine-dibenzofurans 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-dibenzofurans 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-dibenzofurans group Cuprous bromide cluster compound electroluminescent material, testing result are as follows: Exact Mass:2612.10；m/z:2619.10 (100.0%)；Elemental Analysis for C144H104Br4Cu4N4O2P4C,66.01；H,4.00；O,1.22.
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-dibenzofurans 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, purple based on the functional double phosphine cuprous bromide cluster compounds of 4,7- triphenylamine-dibenzofurans group It is absorbed as 281nm, fluorescent emission 500nm outside.As can be seen from Figure 29, using the preparation of embodiment 14 based on 4,7- triphenylamine- The maximum of the electroluminescent device of the double phosphine cuprous bromide cluster compound electroluminescent material preparations of the functionality of dibenzofurans group External quantum efficiency is 7.6%, and maximum current efficiency is 19.8cdA-1, power efficiency 21.5lm/W.
Embodiment 15: manufactured in the present embodiment based on the functional double phosphine iodine of 4,7- triphenylamine-dibenzofurans 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-dibenzofurans 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-dibenzofurans group Cuprous iodide cluster compound electroluminescent material, testing result are as follows: Exact Mass:2804.05；m/z:2807.05 (100.0%)；Elemental Analysis for C144H104I4Cu4N4O2P4:C,61.59；H,3.73；O,1.14.
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-dibenzofurans 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-dibenzofurans group Cuprous iodide cluster compound UV absorption is 280nm, fluorescent emission 510nm.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-dibenzofurans group The maximum external quantum efficiency of luminescent device is 7.7%, and maximum current efficiency is 21.1cdA-1, power efficiency 20.7lm/W.
Embodiment 16: manufactured in the present embodiment functional double based on 4,7- dendroid carbazole-dibenzofurans 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-dibenzofurans 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-dibenzofurans group functionality Double phosphine stannous chloride cluster compound electroluminescent materials, testing result are as follows: Exact Mass:3620.38；m/z:3628.38 (100.0%)；Elemental Analysis for C216H136Cl4Cu4N12O2P4:C,75.17；H,3.97；O,0.93.
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-dibenzofurans 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, embodiment 16 prepare based on 4,7- dendroid carbazole-dibenzofurans group functionality Double phosphine stannous chloride cluster compound UV absorptions are 282nm, fluorescent emission 460nm.As can be seen from Figure 34, it is made using embodiment 16 The functional double phosphine stannous chloride cluster compound electroluminescent material preparations of standby 4,7- dendroid carbazole-dibenzofurans group The maximum external quantum efficiency of electroluminescent device is 6.7%, and maximum current efficiency is 20.1cdA-1, power efficiency is 20.7lm/W。
Embodiment 17: manufactured in the present embodiment functional double based on 4,7- dendroid carbazole-dibenzofurans 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 17 prepare based on the functional double phosphine cuprous bromides of 4,7- dendroid carbazole-dibenzofurans 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-dibenzofurans group functionality Double phosphine cuprous bromide cluster compound electroluminescent materials, testing result are as follows: Exact Mass:3576.43；m/z:3583.43 (100.0%)；Elemental Analysis for C216H136Br4Cu4N12O2P4:C,71.49；H,3.78；O,0.88.
The application test of embodiment 17: this test and the difference of the application test of embodiment one are: in step 4 Be deposited prepared by embodiment 17 on exciton barrier-layer based on the functional double phosphines of 4,7- dendroid carbazole-dibenzofurans group Cuprous bromide 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 32, embodiment 17 prepare based on 4,7- dendroid carbazole-dibenzofurans group functionality Double phosphine cuprous bromide cluster compound UV absorptions are 280nm, fluorescent emission 510nm.As can be seen from Figure 35, it is made using embodiment 17 It is standby based on the functional double phosphine cuprous bromide cluster compound electroluminescent material systems of 4,7- dendroid carbazole-dibenzofurans group The maximum external quantum efficiency of standby electroluminescent device is 8.0%, and maximum current efficiency is 20.6cdA-1, power efficiency is 20.4lm/W。
Embodiment 18: manufactured in the present embodiment functional double based on 4,7- dendroid carbazole-dibenzofurans 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-dibenzofurans 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-dibenzofurans group functionality Double phosphine cuprous iodide cluster compound electroluminescent materials, testing result are as follows: Exact Mass:3812.32；m/z:3816.33 (100.0%)；Elemental Analysis for C216H136I4Cu4N12O2P4:C,67.96；H,3.59；O,0.84.
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-dibenzofurans 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-dibenzofurans group functionality Double phosphine cuprous iodide cluster compound UV absorptions are 281nm, fluorescent emission 520nm.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-dibenzofurans group The maximum external quantum efficiency of standby electroluminescent device is 6.4%, and maximum current efficiency is 16.3cdA-1, power efficiency is 16.2lm/W。
Embodiment 19: manufactured in the present embodiment based on 4,7- dendroid tert-butyl carbazole-dibenzofurans 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 are and embodiment One is identical.
Embodiment 19 prepare based on the functional double phosphine chlorine of 4,7- dendroid tert-butyl carbazole-dibenzofurans 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-dibenzofurans group Functional double phosphine stannous chloride cluster compound electroluminescent materials, testing result are as follows: Exact Mass:4373.64；m/z: 4380.65 (100.0%)；Elemental Analysis for C282H272Cl4Cu4N12O2P4:C,77.31；H,6.26；O, 0.73。
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-dibenzofurans 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-dibenzofurans group Functional double phosphine stannous chloride cluster compound UV absorptions are 281nm, 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-dibenzofurans group The maximum external quantum efficiency of the electroluminescent device of electroluminescent material preparation is 8.0%, and maximum current efficiency is 21.1cdA-1, Power efficiency is 27.4lm/W.
Embodiment 20: manufactured in the present embodiment based on 4,7- dendroid tert-butyl carbazole-dibenzofurans 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 reality It is identical to apply example one.
Embodiment 20 prepare based on the functional double phosphine bromines of 4,7- dendroid tert-butyl carbazole-dibenzofurans 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-dibenzofurans group Functional double phosphine cuprous bromide cluster compound electroluminescent materials, testing result are as follows: Exact Mass:4549.44；m/z: 4558.45 (100.0%)；Elemental Analysis for C282H272Br4Cu4N12O2P4:C,74.29；H,6.01；O, 0.70。
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-dibenzofurans 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-dibenzofurans group Copper cluster UV absorption is 281nm, fluorescent emission 510nm.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-dibenzofurans group The maximum external quantum efficiency of electroluminescence device is 7.8%, and maximum current efficiency is 20.2cdA-1, power efficiency 25.4lm/ W。
Embodiment 21: manufactured in the present embodiment based on 4,7- dendroid tert-butyl carbazole-dibenzofurans 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 are It is the same as example 1.
Embodiment 21 prepare based on the functional double phosphines of 4,7- dendroid tert-butyl carbazole-dibenzofurans 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-dibenzofurans group The double phosphine cuprous iodide cluster compound electroluminescent materials of functionality, testing result is as follows: Exact Mass:4741.39；m/z: 4746.39 (100.0%)；Elemental Analysis for C282H272I4Cu4N12O2P4:C,71.35；H,5.78；O, 0.67。
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-dibenzofurans 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-dibenzofurans group Copper cluster UV absorption is 280nm, fluorescent emission 490nm.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-dibenzofurans group Electroluminescent device maximum external quantum efficiency be 9.1%, maximum current efficiency be 20.4cdA-1, power efficiency is 18.9lm/W。
Embodiment 22: manufactured in the present embodiment based on 4,7- dendroid carbazole diphenylamines-dibenzofurans 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-dibenzofurans 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-dibenzofurans group The double phosphine stannous chloride cluster compound electroluminescent materials of functionality, testing result is as follows: Exact Mass:3460.70；m/z: 3466.71 (100.0%)；Elemental Analysis for C216H152Cl4Cu4N12O2P4:C,74.82；H,4.42；O, 0.92。
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-dibenzofurans 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-dibenzofurans group The double phosphine stannous chloride cluster compound electroluminescent material UV absorptions of functionality be 281nm, fluorescent emission 460nm.From Figure 46 It is found that being prepared using embodiment 22 functional double based on 4,7- dendroid carbazole diphenylamines-dibenzofurans group The maximum external quantum efficiency of the electroluminescent device of phosphine stannous chloride cluster compound electroluminescent material preparation is 8.9%, maximum electricity Stream efficiency is 21.1cdA-1, power efficiency 27.3lm/W.
Embodiment 23: manufactured in the present embodiment based on 4,7- dendroid carbazole diphenylamines-dibenzofurans 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-dibenzofurans 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-dibenzofurans group The double phosphine cuprous bromide cluster compound electroluminescent materials of functionality, testing result is as follows: Exact Mass:3636.50；m/z: 3644.50 (100.0%)；Elemental Analysis for C216H152Br4Cu4N12O2P4:C,71.17；H,4.20；O, 0.88。
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-dibenzofurans 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-dibenzofurans group The double phosphine cuprous bromide cluster compound electroluminescent material UV absorptions of functionality be 280nm, fluorescent emission 510nm.From Figure 47 It is found that being prepared using embodiment 23 functional double based on 4,7- dendroid carbazole diphenylamines-dibenzofurans group The maximum external quantum efficiency of the electroluminescent device of phosphine cuprous bromide cluster compound electroluminescent material preparation is 7.0%, maximum electricity Stream efficiency is 19.9cdA-1, power efficiency 25.5lm/W.
Embodiment 24: manufactured in the present embodiment based on 4,7- dendroid carbazole diphenylamines-dibenzofurans 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-dibenzofurans 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-dibenzofurans group The double phosphine cuprous iodide cluster compound electroluminescent materials of functionality, testing result is as follows: Exact Mass:3828.45；m/z: 3832.45 (100.0%)；Elemental Analysis for C216H152I4Cu4N12O2P4:C,67.68；H,4.00；O, 0.83。
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-dibenzofurans 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-dibenzofurans group The double phosphine cuprous iodide cluster compound electroluminescent material UV absorptions of functionality be 282nm, fluorescent emission 500nm.From Figure 48 It is found that being prepared using embodiment 24 functional double based on 4,7- dendroid carbazole diphenylamines-dibenzofurans group The maximum external quantum efficiency of the electroluminescent device of phosphine cuprous iodide cluster compound electroluminescent material preparation is 7.6%, maximum electricity Stream efficiency is 20.9cdA-1, power efficiency 20.7lm/W.
Embodiment 25: manufactured in the present embodiment based on 4,7- dendroid carbazole triphenylamine-dibenzofurans 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-dibenzofurans 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-dibenzofurans group The double phosphine stannous chloride cluster compound electroluminescent materials of functionality, testing result is as follows: Exact Mass:4101.02；m/z: 4107.02 (100.0%)；Elemental Analysis for C266H192Cl4Cu4N12O2P4:C,77.77；H,4.71；O, 0.78。
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-dibenzofurans 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-dibenzofurans group The double phosphine stannous chloride cluster compound electroluminescent material UV absorptions of functionality be 281nm, fluorescent emission 458nm.From Figure 52 It is found that being prepared using embodiment 25 functional double based on 4,7- dendroid carbazole triphenylamine-dibenzofurans 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-dibenzofurans 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 reality It is identical to apply example one.
Embodiment 26 prepare based on the functional double phosphines of 4,7- dendroid carbazole triphenylamine-dibenzofurans 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-dibenzofurans group The double phosphine cuprous bromide cluster compound electroluminescent materials of functionality, testing result is as follows: Exact Mass:4276.82；m/z: 4284.82 (100.0%)；Elemental Analysis for C266H192Br4Cu4N12O2P4:C,74.54；H,4.52；O, 0.75。
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-dibenzofurans 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-dibenzofurans group The double phosphine cuprous bromide cluster compound electroluminescent material UV absorptions of functionality be 281nm, fluorescent emission 500nm.From Figure 53 It is found that being prepared using embodiment 26 functional double based on 4,7- dendroid carbazole triphenylamine-dibenzofurans group The maximum external quantum efficiency of the electroluminescent device of phosphine cuprous bromide cluster compound electroluminescent material preparation is 8.2%, maximum electricity Stream efficiency is 20.0cdA-1, power efficiency 27.0lm/W.
Embodiment 27: manufactured in the present embodiment based on 4,7- dendroid carbazole triphenylamine-dibenzofurans 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-dibenzofurans 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-dibenzofurans group The double phosphine cuprous iodide cluster compound electroluminescent materials of functionality, testing result is as follows: Exact Mass:4468.76；m/z: 4472.77 (100.0%)；Elemental Analysis for C266H192I4Cu4N12O2P4:C,71.41；H,4.33；O, 0.72。
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-dibenzofurans 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-dibenzofurans group The double phosphine cuprous iodide cluster compound electroluminescent material UV absorptions of functionality be 280nm, fluorescent emission 495nm.From Figure 54 It is found that being prepared using embodiment 27 functional double based on 4,7- dendroid carbazole triphenylamine-dibenzofurans group The maximum external quantum efficiency of the electroluminescent device of phosphine cuprous iodide cluster compound electroluminescent material preparation is 9.3%, maximum electricity Stream efficiency is 20.2cdA-1, power efficiency 27.3lm/W.
From Figure 55, Figure 56 and Figure 57 it is found that electroluminescent peak value is respectively 505nm, 510nm and 515nm.
From Figure 58, Figure 59, Figure 60 it is found that electroluminescent peak value is respectively 505nm, 510nm and 502nm.
From Figure 61, Figure 62, Figure 63 it is found that electroluminescent peak value is respectively 507nm, 515nm and 513nm.
From Figure 64, Figure 65, Figure 66 it is found that electroluminescent peak value is respectively 560nm, 570nm and 520nm.
From Figure 67, Figure 68, Figure 69 it is found that electroluminescent peak value is respectively 515nm, 512nm and 515nm.
From Figure 70, Figure 71, Figure 72 it is found that electroluminescent peak value is respectively 520nm, 520nm and 522nm.
From Figure 73, Figure 74, Figure 75 it is found that electroluminescent peak value is respectively 556m, 570nm and 540nm.
From Figure 76, Figure 77, Figure 78 it is found that electroluminescent peak value is respectively 518nm, 508nm and 515nm.
From Figure 79, Figure 80, Figure 81 it is found that electroluminescent peak value is respectively 5350nm, 542nm and 520nm.

Claims (9)

1. a kind of double phosphine copper cluster electroluminescent materials of functionality based on dibenzofurans group, it is characterised in that Yi Zhongji In the structural formula of the double phosphine copper cluster electroluminescent materials of the functionality of dibenzofurans group are as follows:Its In, 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 dibenzofurans 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 dibenzofurans 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 dibenzofurans 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 electroluminescent materials of a kind of functionality based on dibenzofurans group as claimed in claim 2 Preparation method, it is characterised in that the volume ratio of methylene chloride and petroleum ether in the mixed liquor of the methylene chloride and petroleum ether For 1:20.
4. the double phosphine copper cluster electroluminescent materials of a kind of functionality based on dibenzofurans group as claimed in claim 2 Preparation method, it is characterised in that the mass ratio of the material of the functional biphosphine ligand and cuprous halide be (1~3): 1.
5. the double phosphine copper cluster electroluminescent materials of a kind of functionality based on dibenzofurans group as claimed in claim 2 Preparation method, it is characterised in that the mass ratio of the material of the functional biphosphine ligand and cuprous halide be (2~3): 1.
6. the double phosphine copper cluster electroluminescent materials of a kind of functionality based on dibenzofurans group as claimed in claim 2 Preparation method, it is characterised in that the amount of the substance of the functional biphosphine ligand and the volume ratio of methylene chloride are 1mmol: (3mL~5mL).
7. the double phosphine copper cluster electroluminescent materials of a kind of functionality based on dibenzofurans group as claimed in claim 2 Preparation method, it is characterised in that the amount of the substance of the functional biphosphine ligand and the volume ratio of methylene chloride are 1mmol: (5mL~10mL).
8. the double phosphine copper cluster electroluminescent materials of a kind of functionality based on dibenzofurans group as claimed in claim 2 Preparation method, 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 the mixed of methylene chloride and petroleum ether Closing liquid is that eluent carries out column chromatographic purifying, obtains the double phosphine copper cluster electroluminescent of functionality based on dibenzofurans group Material.
9. the double phosphine copper cluster electroluminescent materials of a kind of functionality based on dibenzofurans 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 dibenzofurans group are as hair Photosphere material is applied in electroluminescent device.
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