CN109928960B - Non-aromatic amine high exciton utilization rate small molecule material and application - Google Patents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention belongs to the field of organic photoelectric materials, and discloses a non-aromatic amine high exciton utilization rate small molecular material and application thereof. The non-aromatic amine high exciton utilization rate small molecular material has a structural general formula shown as a formula (I), wherein R in the formula1、R2And R3Is a donor unit of a thioxanthene, dibenzothiophene or dibenzofuran derivative. The material obtained by the invention has a single structure and definite molecular weight, does not contain the traditional aromatic amine unit, is used for the luminescent layer of an organic luminescent device, and shows greatly improved exciton utilization rate.
Description
Technical Field
The invention belongs to the field of organic photoelectric materials, and particularly relates to a non-aromatic amine high-exciton-utilization small molecular material and application thereof.
Background
Organic Light Emitting Diode (OLED) devices have great application prospects in the fields of flat panel display and solid light sources due to their characteristics of self-luminescence, wide color gamut, wide viewing angle, low energy consumption and the like. Compared with polymer materials, the micromolecule materials are more beneficial to improving the efficiency of organic photoelectric devices due to the advantages of simple synthesis and purification, definite molecular weight, stable structure and the like, and have simpler device preparation technology, thereby realizing the commercial application of the organic light-emitting diode. Thermally Activated Delayed Fluorescence (TADF) materials are based on an intrinsically small singlet triplet energy gap (Delta E)ST) The efficient reverse intersystem crossing (RISC) process in electroluminescence ensures that the electroluminescent material can efficiently utilize high concentration which cannot be utilized by the traditional fluorescent materialTriplet excitons, achieving high Internal Quantum Efficiency (IQE) approaching 100%. Meanwhile, compared with phosphorescent materials utilizing heavy metal atoms, pure organic thermally activated delayed fluorescence organic light emitting diodes (TADF-OLED) have achieved high efficiency similar to that of phosphorescent organic light emitting diodes (PH-OLED), so that the materials show a considerable application prospect.
The donor system has smaller singlet fission energy, is favorable for realizing rapid reverse intersystem crossing, has better carrier balance capability, is favorable for realizing effective bipolar transmission and good carrier balance in device application, and becomes a mainstream scheme for TADF material design. However, the highly efficient donor-acceptor TADF systems reported so far are all based on aromatic amine donor compounds or exciplex systems containing aromatic amine units. However, no organic light-emitting system based on unimolecular non-aromatic amines with high exciton utilization rate has been reported so far. Relates to a non-doped high exciton utilization system which is more beneficial to realizing a high-efficiency stable device.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a non-aromatic amine micromolecule material with high exciton utilization rate.
The invention also aims to provide the application of the non-aromatic amine high-exciton-utilization small-molecule material in an organic photoelectric device.
The purpose of the invention is realized by the following technical scheme:
a non-aromatic amine high exciton utilization rate small molecule material has a structural general formula shown as the following formula (I):
r in the formula (I)1、R2And R3At least one donor substituent selected from any one of the following D1-D4, and the rest is phenyl;
in the formula, R4、R5And R6Each independently selected from S or O.
Preferably, the non-aromatic amine donor-acceptor type small molecule material has a structural formula shown in any one of (1) to (60) below:
the non-aromatic amine high-exciton-utilization small molecular material can be prepared through Suzuki coupling reaction.
The non-aromatic amine high exciton utilization rate small molecular material is applied to an organic photoelectric device.
Preferably, the non-aromatic amine high exciton utilization rate small molecule material is used as a light emitting layer in an organic photoelectric device; the organic photoelectric device comprises a transparent substrate, a transparent anode layer, a plurality of organic light emitting layer units and a cathode layer, wherein the transparent anode layer is formed on the substrate, the organic light emitting layer units comprise a hole injection layer, a hole transmission layer, one or more light emitting layers and an electron transmission layer, and the light emitting layer comprises a single or mixed component non-aromatic amine high-exciton-utilization small molecule material.
The non-aromatic amine high exciton utilization rate small molecular material has the following advantages and beneficial effects:
(1) the small molecular material which is substituted by taking the thioxanthone, the dibenzothiophene and the dibenzofuran derivatives as donors and taking the triphenylpyrimidine derivatives as receptors and does not contain the traditional aromatic amine unit has the advantages of simple structure, determined molecular weight, easy purification, stable electrochemistry and easy research of the structure-activity relationship; the organic thin film can be formed by vacuum evaporation or spin coating, and applied to organic photoelectric devices including organic light emitting diodes and the like.
(2) Compared with 25% of the exciton utilization rate of the traditional fluorescent material, the non-aromatic amine high-exciton-utilization-rate small molecular material provided by the invention is used for the light-emitting layer of the organic light-emitting device, and shows the greatly improved exciton utilization rate (> 80%), and partially shows the property of delayed fluorescence due to thermal activation.
(3) The non-aromatic amine high exciton utilization rate small molecular material can realize effective regulation and control of the light color and efficiency of the material by changing the content of sulfur oxygen atoms and the bonding position of an acceptor unit coupled with the sulfur oxygen atoms, and meets the requirements of organic photoelectric devices.
Drawings
Fig. 1 is a spectrum of absorption, fluorescence emission and phosphorescence emission of the non-aromatic amine type high exciton utilization small molecule material of the structure 1 obtained in example 1 under a solution.
Fig. 2 is a fluorescence emission and phosphorescence emission spectrum of the non-aromatic amine type high exciton utilization rate small molecule material of the structure 5 obtained in example 5 in a powder state.
Fig. 3 is a cyclic voltammogram of the non-aromatic amine high exciton utilization small molecule materials of structure 1 and structure 5 obtained in the examples.
Fig. 4 is a thermogravimetric analysis and differential scanning calorimetry (inset) plot of the non-aromatic amine high exciton utilization small molecule material of structure 1 obtained in example 1.
Fig. 5 is a transient lifetime test chart of the non-aromatic amine type high exciton utilization rate small molecule material of the structure 1 obtained in example 1 under the condition of the non-doped thin film.
FIG. 6 is a graph of transient lifetime measurements under undoped thin film conditions for the non-aromatic amine high exciton utilization small molecule material of structure 5 obtained in example 5;
fig. 7 is a graph of current density-voltage-luminance of a light emitting device obtained based on the non-aromatic amine type high exciton utilization small molecule materials of structure 1 and structure 7 in example 61.
Fig. 8 is an electroluminescence spectrum of a light emitting device obtained based on the non-aromatic amine type high exciton utilization small molecule materials of structure 1 and structure 7 in example 61.
Fig. 9 is a graph of current density-voltage-luminance of a light emitting device obtained based on the non-aromatic amine type high exciton utilization small molecule materials of structure 5 and structure 7 in example 61.
Fig. 10 is an electroluminescence spectrum of a light emitting device obtained based on the non-aromatic amine type high exciton utilization small molecule materials of the structures 5 and 7 in example 61.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material in the structure 1 of the embodiment is as follows:
the specific reaction steps are as follows: thianthrene-1-boronic acid (3.84mmol,1.00g), 2-chloro-4, 6-diphenylpyrimidine (4.22 mmol,1.13g), potassium phosphate (19.20mmol,4.07g), tricyclohexylphosphine (0.31mmol,86mg), Pd2(dba)3(0.192 mmol,176mg) and 100mL of 1, 4-dioxane were sequentially added to the reactor, and after introducing nitrogen for 15min, the mixture was heated at 110 ℃ for reaction for 18 h. After the reaction, when the system is returned to room temperature, dichloromethane and saturated brine are used for extraction, the organic phase is recovered, and the solvent is removed by reduced pressure distillation. The crude product was purified by column chromatography eluting with petroleum ether/dichloromethane 5:1 to give the product of structure 1 in 67% yield. Structure 1 molecular formula: c28H18N2S2(ii) a Molecular weight: 446.59 for m/z; the elemental analysis results were: c, 75.31; h, 4.06; n, 6.27; s, 14.36.
The absorption, fluorescence emission and phosphorescence emission spectrograms of the non-aromatic amine high exciton utilization rate small molecule material of the structure 1 obtained in the embodiment under the solution are shown in fig. 1; the cyclic voltammogram is shown in FIG. 3; thermogravimetric analysis and differential scanning calorimetry (inset) test curves are shown in figure 4; the transient lifetime test pattern under the undoped film condition is shown in fig. 5.
Example 2
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material of structure 2 in this example is as follows:
the specific reaction steps are as follows: compared with the structure 1, the difference is that the thianthrene-1-boric acid is replaced by phenoxathiin-4-boric acid with equivalent weight, and other raw materials and steps are the same as the structure 1. The final product of structure 2 was obtained in 67% yield. Structure 2 molecular formula: c28H18N2An OS; molecular weight: 430.53 for m/z; the elemental analysis results were: c, 78.12; h, 4.21; n, 6.51; o, 3.72; and S, 7.45.
Example 3
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material of structure 3 in this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 1, the difference is that thianthrene-1-boronic acid is replaced by phenoxathiin-1-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 1. The final product of structure 3 was obtained in 67% yield. Structure 3 molecular formula: c28H18N2An OS; molecular weight: 430.53 for m/z; the elemental analysis results were: c, 78.12; h, 4.21; n, 6.51; o, 3.72; and S, 7.45.
Example 4
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material of structure 4 in this example is as follows:
the specific reaction steps are as follows: compared with the structure 1, the difference is that thianthrene-1-boric acid is replaced by dioxin-1-boric acid with equivalent weight, and other raw materials and steps are the same as the structure 1. The final product of structure 4 was obtained in 67% yield. Structure 4 molecular formula: c28H18N2O2(ii) a Molecular weight: 414.46 for m/z; the elemental analysis results were: c, 81.14; h, 4.38; n, 6.76; and O, 7.72.
Example 5
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material in the structure 5 of the embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 1, the difference is that 2-chloro-4, 6-diphenyl pyrimidine is replaced by 4-chloro-2, 6-diphenyl pyrimidine with equivalent weight, and other raw materials and steps are the same as the structure 1. The final product of structure 5 was obtained in 67% yield. Structure 5 molecular formula: c28H18N2S2(ii) a Molecular weight: 446.59 for m/z; the elemental analysis results were: c, 75.31; h, 4.06; n, 6.27; s, 14.36.
The fluorescence emission and phosphorescence emission spectra of the non-aromatic amine high exciton utilization ratio small molecule material with the structure 5 obtained in the embodiment in the powder state are shown in fig. 2; the cyclic voltammogram is shown in FIG. 3; the transient lifetime test pattern under the undoped film condition is shown in fig. 6.
Example 6
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material of structure 6 in this example is as follows:
the specific reaction steps are as follows: compared with the structure 5, the difference is that the thianthrene-1-boric acid is replaced by phenoxathiin-4-boric acid with equivalent weight, and other elementsThe materials and steps are the same as for structure 5. The final product of structure 6 was obtained in 67% yield. Structure 6 molecular formula: c28H18N2An OS; molecular weight: 430.53 for m/z; the elemental analysis results were: c, 78.12; h, 4.21; n, 6.51; o, 3.72; and S, 7.45.
Example 7
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material in the structure 7 of the embodiment is shown as follows:
the specific reaction steps are as follows: compared with the structure 5, the difference is that the thianthrene-1-boronic acid is replaced by phenoxathiin-1-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 5. The final product of structure 7 was obtained in 67% yield. Structure 7 molecular formula: c28H18N2An OS; molecular weight: 430.53 for m/z; the elemental analysis results were: c, 78.12; h, 4.21; n, 6.51; o, 3.72; and S, 7.45.
Example 8
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material of structure 8 in this example is as follows:
the specific reaction steps are as follows: compared with the structure 5, the difference is that thianthrene-1-boric acid is replaced by dioxin-1-boric acid with equivalent weight, and other raw materials and steps are the same as the structure 5. The final product of structure 8 was obtained in 67% yield. Structure 8 molecular formula: c28H18N2O2(ii) a Molecular weight: 414.46 for m/z; the elemental analysis results were: c, 81.14; h, 4.38; n, 6.76; and O, 7.72.
Example 9
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material of structure 9 in this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 1, the difference is that the thianthrene-1-boric acid is replaced by the equivalent thianthrene-2-boric acid, and other raw materials and steps are the same as the structure 1. The final product of structure 9 was obtained in 67% yield. Structure 9 molecular formula: c28H18N2S2(ii) a Molecular weight: 446.59 for m/z; the elemental analysis results were: c, 75.31; h, 4.06; n, 6.27; s, 14.36.
Example 10
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material with the structure 10 in the embodiment is shown as follows:
the specific reaction steps are as follows: compared with the structure 1, the difference is that the thianthrene-1-boric acid is replaced by phenoxathiin-3-boric acid with equivalent weight, and other raw materials and steps are the same as the structure 1. The final product of structure 10 was obtained in 67% yield. Structure 10 molecular formula: c28H18N2An OS; molecular weight: 430.53 for m/z; the elemental analysis results were: c, 78.12; h, 4.21; n, 6.51; o, 3.72; s, 7.45.
Example 11
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material of structure 11 in this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 1, the difference is that the thianthrene-1-boric acid is replaced by phenoxathiin-2-boric acid with equivalent weight, and other raw materials and steps are the same as the structure 1. The final product of structure 11 was obtained in 67% yield. Structure 11 molecular formula: c28H18N2An OS; molecular weight: 430.53 for m/z; the elemental analysis results were: c, 78.12; h, 4.21; n, 6.51; o, 3.72; s, 7.45。
Example 12
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in structure 12 of this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 1, the difference is that thianthrene-1-boric acid is replaced by dioxin-2-boric acid with equivalent weight, and other raw materials and steps are the same as the structure 1. The final product of structure 12 was obtained in 67% yield. Structure 12 molecular formula: c28H18N2O2(ii) a Molecular weight: 414.46 for m/z; the elemental analysis results were: c, 81.14; h, 4.38; n, 6.76; and O, 7.72.
Example 13
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material of structure 13 in this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 5, the difference is that the thianthrene-1-boric acid is replaced by the equivalent thianthrene-2-boric acid, and other raw materials and steps are the same as the structure 5. The final product of structure 13 was obtained in 67% yield. Structure 13 molecular formula: c28H18N2S2(ii) a Molecular weight: 446.59 for m/z; the elemental analysis results were: c, 75.31; h, 4.06; n, 6.27; s, 14.36.
Example 14
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material of structure 14 in this embodiment is as follows:
the specific reaction steps are as follows: compared with structure 13, the difference is that thianthrene-2-boronic acid is usedThe equivalent amount of phenoxathiin-3-boronic acid was changed and the other raw materials and procedures were the same as for structure 13. The final product of structure 14 was obtained in 67% yield. Structure 14 molecular formula: c28H18N2An OS; molecular weight: 430.53 for m/z; the elemental analysis results were: c, 78.12; h, 4.21; n, 6.51; o, 3.72; and S, 7.45.
Example 15
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material in the structure 15 of this embodiment is shown as follows:
the specific reaction steps are as follows: compared with the structure 13, the difference is that the thianthrene-1-boronic acid is replaced by phenoxathiin-2-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 13. The final product of structure 15 was obtained in 67% yield. Structure 15 molecular formula: c28H18N2An OS; molecular weight: 430.53 for m/z; the elemental analysis results were: c, 78.12; h, 4.21; n, 6.51; o, 3.72; and S, 7.45.
Example 16
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 16 of the embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 13, the difference is that thianthrene-1-boronic acid is replaced by dioxin-2-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 13. The final product of structure 16 was obtained in 67% yield. Structure 16 molecular formula: c28H18N2O2(ii) a Molecular weight: 414.46 for m/z; the elemental analysis results were: c, 81.14; h, 4.38; n, 6.76; and O, 7.72.
Example 17
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material in the structure 17 of this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 1, the method is characterized in that thianthrene-1-boric acid is replaced by dibenzothiophene-4-boric acid with equivalent weight, and other raw materials and steps are the same as the structure 1. The final product of structure 17 was obtained in 73% yield. Structure 17 molecular formula: c28H18N2S; molecular weight: 414.53 for m/z; the elemental analysis results were: c, 81.13; h, 4.38; n, 6.76; s, 7.73.
Example 18
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 18 of this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 1, the difference is that the thianthrene-1-boric acid is replaced by the equivalent weight of dibenzofuran-4-boric acid, and other raw materials and steps are the same as the structure 1. The final product of structure 18 was obtained in 61% yield. Structure 18 molecular formula: c28H18N2O; molecular weight: 398.47 for m/z; the elemental analysis results were: c, 84.40; h, 4.55; n, 7.03; and O, 4.02.
Example 19
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material in the structure 19 of the embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 1, the method is characterized in that thianthrene-1-boric acid is replaced by dibenzothiophene-2-boric acid with equivalent weight, and other raw materials and steps are the same as the structure 1. The final product of structure 19 was obtained in 73% yield. Structure 19 molecular formula: c28H18N2S; molecular weight: 414.53 for m/z; yuanThe results of the elemental analysis were: c, 81.13; h, 4.38; n, 6.76; s, 7.73.
Example 20
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material with the structure 20 in this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 1, the difference is that the thianthrene-1-boric acid is replaced by the equivalent weight of dibenzofuran-2-boric acid, and other raw materials and steps are the same as the structure 1. The final product of structure 20 was obtained in 61% yield. Structure 20 molecular formula: c28H18N2O; molecular weight: 398.47 for m/z; the elemental analysis results were: c, 84.40; h, 4.55; n, 7.03; and O, 4.02.
Example 21
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material in the structure 21 of this embodiment is shown as follows:
the specific reaction steps are as follows: compared with the structure 17, the difference is that 2-chloro-4, 6-diphenyl pyrimidine is replaced by 4-chloro-2, 6-diphenyl pyrimidine with equivalent weight, and other raw materials and steps are the same as the structure 17. The final product of structure 21 was obtained in 73% yield. Structure 21 molecular formula: c28H18N2S; molecular weight: 414.53 for m/z; the elemental analysis results were: c, 81.13; h, 4.38; n, 6.76; s, 7.73.
Example 22
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 22 of this embodiment is as follows:
the specific reaction steps are as follows: and knotStructure 21 is compared with the equivalent dibenzothiophene-4-boronic acid to the equivalent dibenzofuran-4-boronic acid, and the other raw materials and steps are the same as structure 21. The final product of structure 22 was obtained in 61% yield. Structure 22 molecular formula: c28H18N2O; molecular weight: 398.47 for m/z; the elemental analysis results were: c, 84.40; h, 4.55; n, 7.03; and O, 4.02.
Example 23
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 23 of this embodiment is as follows:
the specific reaction steps are as follows: compared with structure 21, the method is different in that dibenzothiophene-4-boric acid is replaced by equivalent dibenzothiophene-2-boric acid, and other raw materials and steps are the same as those of structure 21. The final product of structure 23 was obtained in 73% yield. Structure 23 molecular formula: c28H18N2S; molecular weight: 414.53 for m/z; the elemental analysis results were: c, 81.13; h, 4.38; n, 6.76; s, 7.73.
Example 24
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 24 of this embodiment is shown as follows:
the specific reaction steps are as follows: compared with the structure 21, the difference is that dibenzothiophene-4-boric acid is replaced by equivalent dibenzofuran-2-boric acid, and other raw materials and steps are the same as the structure 21. The final product of structure 24 was obtained in 61% yield. Structure 24 molecular formula: c28H18N2O; molecular weight: 398.47 for m/z; the elemental analysis results were: c, 84.40; h, 4.55; n, 7.03; and O, 4.02.
Example 25
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material of structure 25 in this embodiment is as follows:
the specific reaction steps are as follows: compared with structure 13, the difference is that 2, 4-dichloro-6-phenyl-1, 3, 5-triazine is replaced by 2, 4-dichloro-6-phenylpyrimidine with equivalent weight, and other raw materials and steps are the same as structure 13. The final product of structure 61 was obtained in 67% yield. Structure 61 molecular formula: c34H20N2S4(ii) a Molecular weight: 584.79 for m/z; the elemental analysis results were: c, 69.83; h, 3.45; n, 4.79; s, 21.93.
Example 26
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 26 of this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 25, the difference is that the thianthrene-1-boronic acid is replaced by phenoxathiin-4-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 25. The final product of structure 26 was obtained in 59% yield. Structure 26 molecular formula: c34H20N2O2S2(ii) a Molecular weight: 552.67 for m/z; the elemental analysis result was C, 73.89; h, 3.65; n, 5.07; o, 5.79; and S, 11.60.
Example 27
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 27 of this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 25, the difference is that the thianthrene-1-boronic acid is replaced by phenoxathiin-1-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 25. The final product of structure 27 was obtainedThe yield was 42%. Structure 27 molecular formula: c34H20N2O2S2(ii) a Molecular weight: 552.67 for m/z; the elemental analysis result was C, 73.89; h, 3.65; n, 5.07; o, 5.79; and S, 11.60.
Example 28
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material in the structure 28 of this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 25, the difference is that thianthrene-1-boronic acid is replaced by dioxin-1-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 25. The final product of structure 28 was obtained in 59% yield. Structure 28 molecular formula: c34H20N2O4(ii) a Molecular weight: 520.54 for m/z; the elemental analysis results were: c, 78.45; h, 3.87; n, 5.38; o, 12.29.
Example 29
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material in the structure 29 of this embodiment is as follows:
the specific reaction steps are as follows: compared with structure 25, except that 2, 4-dichloro-6-phenylpyrimidine was replaced with an equivalent amount of 4, 6-dichloro-2-phenylpyrimidine, the other starting materials and procedures were the same as in structure 25. The final product was obtained in 67% yield for structure 29. Structure 29 molecular formula: c34H20N2S4(ii) a Molecular weight: 584.79 for m/z; the elemental analysis results were: c, 69.83; h, 3.45; n, 4.79; s, 21.93.
Example 30
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material of the structure 30 in this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 29, the difference is that thianthrene-1-boronic acid is replaced by phenoxathiin-4-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 29. The final product of structure 30 was obtained in 59% yield. Structure 30 molecular formula: c34H20N2O2S2(ii) a Molecular weight: 552.67 for m/z; the elemental analysis result was C, 73.89; h, 3.65; n, 5.07; o, 5.79; and S, 11.60.
Example 31
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material of the structure 31 in this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 26, the difference is that the thianthrene-1-boronic acid is replaced by phenoxathiin-1-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 26. The final product was obtained in 42% yield for structure 31. Structure 31 molecular formula: c34H20N2O2S2(ii) a Molecular weight: 552.67 for m/z; elemental analysis results were C, 73.89; h, 3.65; n, 5.07; o, 5.79; and S, 11.60.
Example 32
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material of structure 32 in this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 26, the difference is that thianthrene-1-boronic acid is replaced by dioxin-1-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 26. The final product of structure 32 was obtained in 59% yield. Structure 32 molecular formula: c34H20N2O4(ii) a Molecular weight: 520.54 for m/z; yuanThe results of the elemental analysis were: c, 78.45; h, 3.87; n, 5.38; o, 12.29.
Example 33
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material of the structure 33 in this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 25, the difference is that the thianthrene-1-boronic acid is replaced by the equivalent thianthrene-2-boronic acid, and other raw materials and steps are the same as the structure 25. The final product of structure 33 was obtained in 59% yield. Structure 33 molecular formula: c34H20N2S4(ii) a Molecular weight: 584.79 for m/z; the elemental analysis results were: c, 69.83; h, 3.45; n, 4.79; s, 21.93.
Example 34
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 34 of this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 25, the difference is that the thianthrene-1-boronic acid is replaced by phenoxathiin-3-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 25. The final product of structure 34 was obtained in 73% yield. Structure 34 molecular formula: c34H20N2O2S2(ii) a Molecular weight: 552.67 for m/z; the elemental analysis result was C, 73.89; h, 3.65; n, 5.07; o, 5.79; and S, 11.60.
Example 35
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 35 of this embodiment is as follows:
concretely, the reverseThe method comprises the following steps: compared with the structure 25, the difference is that the thianthrene-1-boronic acid is replaced by phenoxathiin-2-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 25. The final product was obtained in 40% yield from structure 35. Structure 35 molecular formula: c34H20N2O2S2(ii) a Molecular weight: 552.67 for m/z; the elemental analysis result was C, 73.89; h, 3.65; n, 5.07; o, 5.79; and S, 11.60.
Example 36
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 36 of this embodiment is as follows:
the specific reaction steps are as follows: compared with structure 25, the difference is that thianthrene-1-boronic acid is replaced by equivalent amount of dioxin-2-boronic acid, and other raw materials and steps are the same as structure 25. The final product of structure 36 was obtained in 39% yield. Structure 36 molecular formula: C34H20N2O 4; molecular weight: 520.54 for m/z; the elemental analysis results were: c, 78.45; h, 3.87; n, 5.38; o, 12.29.
Example 37
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material of the structure 37 in this embodiment is as follows:
the specific reaction steps are as follows: compared with structure 33, the difference is that 2, 4-dichloro-6-phenylpyrimidine is replaced with an equivalent amount of 4, 6-dichloro-2-phenylpyrimidine, and the other starting materials and steps are the same as in structure 33. The final product was obtained in 67% yield for structure 37. Structure 37 molecular formula: c34H20N2S4(ii) a Molecular weight: 584.79 for m/z; the elemental analysis results were: c, 69.83; h, 3.45; n, 4.79; s, 21.93.
Example 38
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 38 of this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 37, the difference is that the thianthrene-2-boronic acid is replaced by phenoxathiin-3-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 37. The final product was obtained in 59% yield for structure 38. Structure 38 molecular formula: c34H20N2O2S2(ii) a Molecular weight: 552.67 for m/z; the elemental analysis result was C, 73.89; h, 3.65; n, 5.07; o, 5.79; and S, 11.60.
Example 39
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 39 of this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 37, the difference is that the thianthrene-2-boronic acid is replaced by phenoxathiin-2-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 37. The final product was obtained in 42% yield from structure 39. Structure 39 molecular formula: c34H20N2O2S2(ii) a Molecular weight: 552.67 for m/z; the elemental analysis result was C, 73.89; h, 3.65; n, 5.07; o, 5.79; and S, 11.60.
Example 40
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material of the structure 40 in this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 37, the difference is that the thianthrene-2-boronic acid is replaced by the equivalent weight of dioxin-2-boronic acid, and other raw materials and steps are the same as the structure 37. Finally obtaining the knotConstruct 40, 59% yield. Structure 40 molecular formula: c34H20N2O4(ii) a Molecular weight: 520.54 for m/z; the elemental analysis results were: c, 78.45; h, 3.87; n, 5.38; o, 12.29.
EXAMPLE 41
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 41 of this embodiment is as follows:
the specific reaction steps are as follows: compared with structure 25, the difference is that thianthrene-1-boronic acid is replaced by dibenzothiophene-4-boronic acid with equivalent weight, and other raw materials and steps are the same as structure 25. The final product of structure 41 was obtained in 76% yield. Structure 41 molecular formula: c34H20N2S2(ii) a Molecular weight: 520.67 for m/z; the elemental analysis results were: c, 78.43; h, 3.87; n, 5.38; s, 12.31.
Example 42
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 42 of this embodiment is as follows:
the specific reaction steps are as follows: compared with structure 25, the difference is that thianthrene-1-boronic acid is replaced by dibenzofuran-4-boronic acid with equivalent weight, and other raw materials and steps are the same as structure 25. The final product of structure 42 was obtained in 62% yield. Structure 42 molecular formula: c34H20N2O2(ii) a Molecular weight: 488.55 for m/z; the elemental analysis results were: c, 83.59; h, 4.13; n, 5.73; and O, 6.55.
Example 43
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material in structure 43 of this embodiment is as follows:
the specific reaction steps are as follows: compared with structure 25, the difference is that thianthrene-1-boronic acid is replaced by dibenzothiophene-2-boronic acid with equivalent weight, and other raw materials and steps are the same as structure 25. The final product of structure 43 was obtained in 73% yield. Structure 43 formula: c34H20N2S2(ii) a Molecular weight: 520.67 for m/z; the elemental analysis results were: c, 78.43; h, 3.87; n, 5.38; s, 12.31.
Example 44
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material of the structure 44 in this embodiment is as follows:
the specific reaction steps are as follows: compared with structure 25, the difference is that thianthrene-1-boronic acid is replaced by dibenzofuran-2-boronic acid with equivalent weight, and the other raw materials and steps are the same as structure 25. The final product was obtained in 61% yield for structure 44. Structure 44 molecular formula: c34H20N2O2(ii) a Molecular weight: 488.55 for m/z; the elemental analysis results were: c, 83.59; h, 4.13; n, 5.73; and O, 6.55.
Example 45
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material of structure 45 in this embodiment is as follows:
the specific reaction steps are as follows: compared with structure 41, the difference is that 2, 4-dichloro-6-phenylpyrimidine is replaced with an equivalent amount of 4, 6-dichloro-2-phenylpyrimidine and the other starting materials and steps are the same as in structure 41. The final product was obtained in 76% yield from structure 45. Structure 45 molecular formula: c34H20N2S2(ii) a Molecular weight: 520.67 for m/z; the elemental analysis results were:C,78.43；H,3.87；N,5.38； S,12.31。
example 46
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material of structure 46 in this embodiment is as follows:
the specific reaction steps are as follows: compared with structure 45, the difference is that dibenzothiophene-4-boric acid is replaced by dibenzofuran-4-boric acid with equivalent weight, and other raw materials and steps are the same as structure 45. The final product was obtained in 62% yield for structure 46. Structure 46 molecular formula: c34H20N2O2(ii) a Molecular weight: 488.55 for m/z; the elemental analysis results were: c, 83.59; h, 4.13; n, 5.73; and O, 6.55.
Example 47
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material of structure 47 in this embodiment is as follows:
the specific reaction steps are as follows: compared with structure 45, the difference is that dibenzothiophene-4-boronic acid is replaced by dibenzothiophene-2-boronic acid with equivalent weight, and other raw materials and steps are the same as those of structure 45. The final product was obtained in 73% yield for structure 47. Structure 47 molecular formula: c34H20N2S2(ii) a Molecular weight: 520.67 for m/z; the elemental analysis results were: c, 78.43; h, 3.87; n, 5.38; s, 12.31.
Example 48
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material of structure 48 in this embodiment is as follows:
specific reaction procedureThe following were used: compared with structure 45, the difference is that dibenzothiophene-4-boric acid is replaced by equivalent dibenzofuran-2-boric acid, and other raw materials and steps are the same as structure 45. The final product was obtained in 61% yield from structure 48. Structure 48 molecular formula: c34H20N2O2(ii) a Molecular weight: 488.55 for m/z; the elemental analysis results were: c, 83.59; h, 4.13; n, 5.73; and O, 6.55.
Example 49
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 49 of this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 25, the difference is that cyanuric chloride is replaced by equivalent 2,4, 6-trichloropyrimidine, and other raw materials and steps are the same as the structure 25. The final product was obtained in 67% yield for structure 49. Structure 49 molecular formula: c40H22N2S6(ii) a Molecular weight: 722.99 for m/z; the elemental analysis results were: c, 66.45; h, 3.07; n, 3.87; and S, 26.61.
Example 50
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material with the structure 50 in the embodiment is shown as follows:
the specific reaction steps are as follows: compared with the structure 49, the difference is that the thianthrene-1-boronic acid is replaced by phenoxathiin-4-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 49. The final product was obtained in 57% yield with structure 50. Structure 50 molecular formula: c40H22N2O3S3(ii) a Molecular weight: 674.81 for m/z; the elemental analysis results were: c, 71.20; h, 3.29; n, 4.15; o, 7.11; and S, 14.25.
Example 51
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material of structure 51 in this embodiment is shown as follows:
the specific reaction steps are as follows: compared with the structure 49, the difference is that the thianthrene-1-boronic acid is replaced by phenoxathiin-1-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 49. The final product was obtained in 56% yield from structure 51. Structure 51 molecular formula: c40H22N2O3S3(ii) a Molecular weight: 674.81 for m/z; the elemental analysis results were: c, 71.20; h, 3.29; n, 4.15; o, 7.11; and S, 14.25.
Example 52
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material of the structure 52 in this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 49, the difference is that thianthrene-1-boronic acid is replaced by dioxin-1-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 49. The final product of structure 52 was obtained in 43% yield. Structure 52 molecular formula: c40H22N2O6(ii) a Molecular weight: 626.62 for m/z; the elemental analysis results were: c, 76.67; h, 3.54; n, 4.47; o, 15.32.
Example 53
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material in the structure 53 of this embodiment is shown as follows:
the specific reaction steps are as follows: compared with structure 49, the difference is that thianthrene-1-boronic acid is replaced by equal amount of thianthrene-2-boronic acid, and the other raw materials and steps are the same as structure 49. Most preferablyThe final product was obtained in 67% yield for structure 53. Structure 53 molecular formula: c40H22N2S6(ii) a Molecular weight: 722.99 for m/z; the elemental analysis results were: c, 66.45; h, 3.07; n, 3.87; and S, 26.61.
Example 54
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 54 of this embodiment is as follows:
the specific reaction steps are as follows: compared with structure 49, the difference is that thianthrene-1-boronic acid is replaced by phenoxathiin-2-boronic acid of equivalent weight, and the other raw materials and steps are the same as structure 49. The final product was obtained in 73% yield from structure 54. Structure 54 molecular formula: c40H22N2O3S3(ii) a Molecular weight: 674.81 for m/z; the elemental analysis results were: c, 71.20; h, 3.29; n, 4.15; o, 7.11; s, 14.25.
Example 55
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material in the structure 55 of this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 49, the difference is that the thianthrene-1-boronic acid is replaced by phenoxathiin-2-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 49. The final product was obtained in 56% yield from structure 55. Structure 55 molecular formula: c40H22N2O3S3(ii) a Molecular weight: 674.81 for m/z; the elemental analysis results were: c, 71.20; h, 3.29; n, 4.15; o, 7.11; and S, 14.25.
Example 56
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material of the structure 56 in this embodiment is as follows:
the specific reaction steps are as follows: compared with the structure 49, the difference is that thianthrene-1-boronic acid is replaced by dioxin-1-boronic acid with equivalent weight, and other raw materials and steps are the same as the structure 49. The final product was obtained in 43% yield for structure 56. Structure 56 molecular formula: c40H22N2O6(ii) a Molecular weight: 626.62 for m/z; the elemental analysis results were: c, 76.67; h, 3.54; n, 4.47; o, 15.32.
Example 57
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material of the structure 57 in this embodiment is as follows:
the specific reaction steps are as follows: compared with structure 49, the difference is that thianthrene-1-boronic acid is replaced by dibenzothiophene-4-boronic acid with equivalent weight, and the other raw materials and steps are the same as structure 49. The final product was obtained in 63% yield from structure 57. Structure 57 molecular formula: c40H22N2S3(ii) a Molecular weight: 626.81 for m/z; the elemental analysis results were: c, 76.65; h, 3.54; n, 4.47; s, 15.34.
Example 58
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material with the structure 58 in the embodiment is as follows:
the specific reaction steps are as follows: compared with structure 25, the difference is that thianthrene-1-boronic acid is replaced by dibenzofuran-4-boronic acid with equivalent weight, and other raw materials and steps are the same as structure 25. The final product of structure 34 was obtained in 54% yield. Structure 34 molecular formula: c40H22N2O3(ii) a Molecular weight: 578.63 m/z(ii) a The elemental analysis results were: c, 83.03; h, 3.83; n, 4.84; and O, 8.29.
Example 59
The reaction formula of the non-aromatic amine type high exciton utilization rate small molecule material in the structure 59 of the embodiment is as follows:
the specific reaction steps are as follows: compared with structure 49, the difference is that thianthrene-1-boronic acid is replaced by dibenzothiophene-2-boronic acid with equivalent weight, and the other raw materials and steps are the same as structure 49. The final product was structure 59 in 63% yield. Structure 59 molecular formula: c40H22N2S3(ii) a Molecular weight: 626.81 for m/z; the elemental analysis results were: c, 76.65; h, 3.54; n, 4.47; s, 15.34.
Example 60
The reaction formula of the non-aromatic amine high exciton utilization rate small molecule material with the structure 60 in this embodiment is shown as follows:
the specific reaction steps are as follows: compared with structure 49, the difference is that thianthrene-1-boronic acid is replaced by dibenzofuran-2-boronic acid with equivalent weight, and the other raw materials and steps are the same as structure 49. The final product was obtained in 54% yield from structure 60. Structure 60 molecular formula: c40H22N2O3(ii) a Molecular weight: 578.63 for m/z; the elemental analysis results were: c, 83.03; h, 3.83; n, 4.84; and O, 8.29.
Example 61
In this embodiment, an organic light emitting diode device based on a non-aromatic amine type small molecule material with high exciton utilization rate has a specific stacked structure as follows:
glass substrate/ITO/hole transport layer/light emitting layer/electron transport layer/LiF/Al. ITO is used as anode, and non-aromatic amine high exciton utilization rate small molecule material in the above embodiment is used asThe compound has a small Delta E for a light-emitting layerSTThe electron transport material is an electron transport layer, LiF is used as an electron injection layer, and Al is used as a cathode.
The preparation steps of the light emitting device with the laminated structure are as follows:
and ultrasonically cleaning the ITO transparent conductive glass for 15 minutes by using acetone, a micron-sized special semiconductor detergent, deionized water and isopropanol in sequence to remove dirt on the surface of the substrate. Then drying the ITO substrate in a thermostat at 80 ℃, treating the dried ITO substrate for 3 minutes by using oxygen plasma glow starting equipment, placing the ITO substrate in a vacuum chamber, and carrying out vacuum treatment in a vacuum condition of 1 multiplied by 10-5～9×10-4Under Pa, in the presence of
The deposition rate of the organic material layer is evaporated on the anode film, then the luminescent layer is evaporated, the No. 1-20 material and the electron transmission material are respectively placed on two evaporation sources, and the mixing proportion of the two materials is controlled by a certain deposition rate. Then is followed by
Depositing LiF at a deposition rate to
The Al electrode was evaporated at the deposition rate of (3) to obtain the organic light emitting diode device of the present example.
The CIE color coordinate values of the OLED device obtained by using the non-aromatic amine type high exciton utilization rate small molecule material with the structure 1 obtained in example 1 as the light emitting layer are (0.24, 0.38), the maximum external quantum efficiency is 6.31%, and the exciton utilization rate is-84.1%, which significantly exceeds the maximum exciton utilization rate value (25%) obtained based on the conventional fluorescent material. The basic characterization data are shown in table 1:
TABLE 1
Table 2 shows the necessary energy levels, photophysical properties, and thermodynamic properties of the non-aromatic amine high exciton utilization small molecule material of structure 1 as a light emitting host material.
TABLE 2
The graph of the current density-voltage-luminance graph and the electroluminescence spectrum of the light emitting device obtained by the non-aromatic amine type high exciton utilization rate small molecule material based on the structure 1 and the structure 7 in the embodiment are respectively shown in fig. 7 and fig. 8.
The graph of the current density-voltage-luminance graph and the electroluminescence spectrum of the light emitting device obtained by the non-aromatic amine type high exciton utilization rate small molecule material based on the structure 5 and the structure 7 in the embodiment are respectively shown in fig. 9 and fig. 10.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (3)
1. A non-aromatic amine high exciton utilization rate small molecule material is characterized by having a structural formula shown in any one of the following (1) to (16):
2. use of the non-aromatic amine high exciton utilization small molecule material of claim 1 in an organic optoelectronic device.
3. Use according to claim 2, characterized in that: the organic photoelectric device comprises a transparent substrate, a transparent anode layer, a plurality of organic light emitting layer units and a cathode layer, wherein the transparent anode layer, the plurality of organic light emitting layer units and the cathode layer are formed on the substrate, the organic light emitting layer units comprise a hole injection layer, a hole transport layer, one or more light emitting layers and an electron transport layer, and the light emitting layer comprises a single or mixed component non-aromatic amine high-exciton-utilization small molecule material.
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| US20150171340A1 (en) * | 2013-12-17 | 2015-06-18 | Samsung Electronics Co., Ltd. | Condensed cyclic compound and organic light-emitting device including the same |
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| CN105636959A (en) * | 2013-10-08 | 2016-06-01 | 默克专利有限公司 | Materials for electronic devices |
| US20150171340A1 (en) * | 2013-12-17 | 2015-06-18 | Samsung Electronics Co., Ltd. | Condensed cyclic compound and organic light-emitting device including the same |
| CN106255687A (en) * | 2014-04-30 | 2016-12-21 | 默克专利有限公司 | Material for electronic device |
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