CN108250246B - Four-coordination manganese compound with bipolar structure and preparation method and application thereof - Google Patents
Four-coordination manganese compound with bipolar structure and preparation method and application thereof Download PDFInfo
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- 150000002697 manganese compounds Chemical class 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title abstract description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 46
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- -1 diphenylphosphine compound Chemical class 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 239000011572 manganese Substances 0.000 claims abstract description 10
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
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- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 6
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- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
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- 241000282414 Homo sapiens Species 0.000 description 1
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- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
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- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/20—Multistable switching devices, e.g. memristors
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- Inorganic Chemistry (AREA)
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- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to a preparation method of a four-coordination manganese compound with a bipolar structure, which comprises the following steps: uniformly mixing the raw material A with N, N, N ', N' -tetramethylethylenediamine to obtain a mixed system, and dropwise adding N-butyllithium into the mixed system to perform lithiation reaction to obtain a mixture B; dropwise adding diphenylphosphine chloride into the mixture B for a phosphating reaction to obtain a diphenylphosphine compound; dissolving diphenylphosphine compound in dichloromethane system, adding 30% H2O2To obtain diphenyl phosphine oxide compounds; reacting the diphenyl phosphine oxide compound with manganese dihalide to obtain the four-coordination manganese compound. The invention has the advantages of low price, capability of replacing noble metal iridium complexes as luminescent layer materials to prepare organic light-emitting diodes and reduction of the manufacturing cost of the luminescent materials.
Description
Technical Field
The invention relates to a novel four-coordination manganese compound with a bipolar structure, and a preparation method and application thereof, and belongs to the technical field of organic photoelectric functional materials.
Background
With the improvement of the viewing demand and the visual enjoyment of human beings, the existing display technology cannot meet the higher requirements of people on display equipment, so that the search for a display device which is updated, has higher efficiency, higher performance and lower cost becomes the pursuit target of people. Organic light-emitting diodes (OLEDs) have excellent performances of low power consumption, easy bending, fast response speed, wide viewing angle, capability of large-area display, complete luminescent colors in the aspect of display, potential application value and wide application prospect in the aspect of solid-state lighting, and make OLEDs be widely paid attention to in academic and industrial fields.
Fluorescent OLEDs limit the enhancement of device performance to some extent by utilizing only 25% singlet excitons in internal quantum efficiency. However, recently reported Phosphorescent organic light-emitting diodes (oleds) can theoretically achieve 100% utilization of internal quantum efficiency through internal conversion of excitons. However, at higher currents, phosphorescent dyes are mostly complexes containing heavy metals, such as platinum, ruthenium, iridium, etc., and thus easily cause quenching of Triplet-Triplet excitons (TTA). This requires a suitable host material in which the phosphorescent dye is uniformly distributed to reduce the TTA effect. Suitable host materials are generally required to have a high triplet energy level, a suitable Highest Occupied Molecular Orbital (HOMO), a Lowest Unoccupied Molecular Orbital (LUMO), good carrier balance and high thermal stability.
In recent years, the research of triphenylphosphine oxide group in synthesizing electroluminescent materials attracts the attention of a large number of scholars. Due to the nature of the phosphorus atom, five covalent bonds can be formed, so that the phosphine oxide functional group is easy to be connected with other groups to form a derivative taking the phosphine oxide functional group as a core. Because the oxygen atom has strong electronegativity, the phosphine oxide structure is highly polarized and has strong electron-withdrawing property. The triphenylphosphine oxide unit formed by connecting the electron-withdrawing phosphine oxide group with the benzene ring also has stronger electron withdrawing property, and the electron withdrawing property also has obvious influence on the energy level structure of the formed compound. A novel design idea for the structural design of the host material of PhOLEDs is that triphenylphosphine oxide is used for bridging other groups, the electron-withdrawing characteristic of the triphenylphosphine oxide structure is utilized, and a bipolar host material can be constructed by introducing a certain proportion and number of electron-rich groups, so that the device structure is simplified.
Recent studies have shown that many manganese compounds have strong photoluminescence quantum efficiency and varied emission colors, such as green, yellow, orange, and red light. The luminescence of the manganese compound results from the d-d orbital transition of its metal center. Manganese compounds having a tetrahedral structure generally emit green light, and manganese compounds having an octahedral structure generally emit red light. The higher luminous quantum efficiency makes it a very potential organic photoelectric functional material. It is well known that manganese compounds with a strong green emission are generally composed of inorganic manganese tetrahalide anions and organic cations. However, such ionic four-coordinate manganese compounds like salts are easily deliquesced by water in air to cause luminescence quenching, and have poor stability. Generally, the neutral manganese compound with the bipolar charge transport material is prepared by introducing manganese dihalide into a triphenylphosphine oxide structure bridged compound rich in electron-rich groups and having an electron transport property. Such manganese compounds have strong luminescence quantum efficiency and are very stable in air. Can be used as a main luminescent material and an electron transport material in a device and effectively simplifies the structure of the device. However, manganese compounds having a bipolar structure are rare, and their use in electroluminescent devices has not been reported.
Disclosure of Invention
The invention aims to: aiming at the defects in the prior art, the novel four-coordination manganese compound with a bipolar structure is provided, and the preparation method and the application thereof are provided.
In order to achieve the above object, the present invention provides a four-coordinate manganese compound having a bipolar structure, the four-coordinate manganese compound having a general structural formula as follows:
wherein X is O or S; y is F, Cl, Br, I or SCN (thiocyanato); r is CnH2n+1N is an integer of 0 to 18; r' is H or C (CH)3)3。
According to the invention, through the research on the aspects of molecular structure performance of the compound, introduction of a bipolar structure, manganese chelation, influence of a substituent on material performance and the like, a novel manganese compound with the bipolar structure is designed and synthesized, and a bifunctional material with specific good luminescence performance and electron transmission performance is further constructed. The novel four-coordination manganese compound with a bipolar structure is prepared by introducing manganese dihalide into a compound rich in electron-rich groups and bridged by a triphenylphosphine oxide structure with an electron transmission characteristic, wherein a pi conjugated framework of the compound is formed by bridging the electron-rich groups and the triphenylphosphine oxide structure, and a P ═ O group on a conjugated main chain of the compound and adjacent manganese dihalide can form intramolecular coordination, so that a neutral manganese compound with the bipolar charge transmission material is formed, and the compound is a first novel luminous manganese compound with the bipolar structure. The tetradentate manganese compound (DBFDPO-MnBr)2) The organic photoelectric functional material is generally solid and poor in solubility, can emit weak blue light in a solution state, has strong green light emission in a solid state, has a very potential organic photoelectric functional material, and can be used as a luminescent material and an electrophosphorescent material applied to organic electrophosphorescent devices (PhOLEDs).
The invention also provides a preparation method of the four-coordination manganese compound with the bipolar structure, which comprises the following steps:
first step, preparation: according to a molar ratio of 1: (3-3.5): (3-3.5): (3-6) taking the raw materials A, N-butyllithium (N-BuLi), N, N, N ', N' -Tetramethylethylenediamine (TMEDA) and diphenyl phosphorus chloride (Ph)2PCl) for standby;
step two, lithiation reaction: uniformly mixing the raw material A and N, N, N ', N' -tetramethylethylenediamine to obtain a mixed system, dissolving the mixed system in a dry solvent system, dropwise adding N-butyllithium into the mixed system at the temperature of minus 78 +/-5 ℃ under the protection of nitrogen to perform lithiation reaction, and reacting at normal temperature for 12-18 hours to obtain a mixture B;
step three, phosphating reaction: dropwise adding diphenylphosphine chloride into the mixture B for a phosphating reaction at the temperature of 78 +/-5 ℃ under the protection of nitrogen, and reacting for 12-18 hours at normal temperature to obtain a diphenylphosphine compound;
step four, oxidation reaction: dissolving a diphenylphosphine compound in a dichloromethane system, and adding 3-15 mL of 30% H by mass fraction2O2Stirring and reacting for 4-10 hours at room temperature to obtain a diphenylphosphine oxide compound;
the fifth step is to react the diphenylphosphine oxide with a manganese dihalide (MnY)2) According to a molar ratio of 1: (1-2), dissolving the mixture in a dichloromethane or ethanol solvent system, reacting for 2-6 hours at normal temperature or 70 +/-5 ℃, performing suction filtration, washing by using dichloromethane, and drying to obtain the green light-emitting four-coordinate manganese compound.
Preferably, the raw material A is a dibenzo compound with a chemical formula
The chemical formula of the diphenyl phosphine oxide compound is
The chemical formula of the four-coordination manganese compound is
Wherein X is O or S, and Y is F, Cl, Br, I or SCN.
Preferably, the raw material A is a carbazole compound with a chemical formula
The chemical formula of the diphenyl phosphine oxide compound is
The chemical formula of the four-coordination manganese compound is
Wherein R is CnH2n+1N is an integer of 0 to 18; r' is H or C (CH)3)3And Y is F, Cl, Br, I or SCN.
Preferably, the raw material A is a fluorene compound with a chemical formula
The chemical formula of the diphenyl phosphine oxide compound is
The chemical formula of the four-coordination manganese compound is
Wherein R is CnH2n+1N is an integer of 0 to 18; r' is H or C (CH)3)3And Y is F, Cl, Br, I or SCN.
Preferably, in the second step, the dried solvent system is an ether solvent system, and the amount of the ether solvent system in the reaction process is 30-60 mL; in the fourth step, the reaction dosage of a dichloromethane system is 15-50 mL; in the fifth step, the reaction dosage of the dichloromethane solvent system is 15-50 mL, and the reaction dosage of the ethanol solvent system is 15-50 mL.
Preferably, in the third step, after the product of the phosphating reaction is extracted by water and dichloromethane, an organic layer is taken and is prepared by anhydrous NaSO4Drying to obtain the solid diphenylphosphine compound.
The invention provides an application of a four-coordination manganese compound with a bipolar structure, wherein the four-coordination manganese compound is used as a luminescent material.
The invention provides an application of a four-coordination manganese compound with a bipolar structure, wherein the four-coordination manganese compound is applied to organic electrophosphorescent devices (PhOLEDs) as an electrophosphorescent material; the organic electrophosphorescent device comprises a first electrode, a second electrode and at least one organic functional layer formed between the first electrode and the second electrode, wherein the organic functional layer contains a four-coordinate manganese compound.
The invention provides application of a four-coordination manganese compound with a bipolar structure, wherein the four-coordination manganese compound is used as an organic storage material.
The invention has the advantages that the framework of the novel four-coordination manganese compound has stronger planarity and rigidity, thereby providing attractive photophysical properties, such as strong green light emission, strong phosphorescence emission, high luminous quantum efficiency, high thermal stability and high carrier mobility in a solid state, and obtaining a main body luminous material and an electron transport material with better properties, and the main body luminous material and the electron transport material are applied to a device and can effectively simplify the structure of the device. Meanwhile, the four-coordination phosphorescent manganese compound has low price, can replace a noble metal iridium complex to be used as a luminescent layer material for preparing an organic light-emitting diode, and reduces the manufacturing cost of the luminescent material.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is an absorption spectrum of a four-coordinated manganese compound according to example one or two of the present invention.
FIG. 2 shows the excitation and emission spectra of the four-coordinate manganese compounds of examples I and II of the present invention.
FIG. 3 is a solid state luminescence lifetime spectrum of a four-coordinate manganese compound according to example one of the present invention.
FIG. 4 is a solid state luminescence lifetime spectrum of a four-coordinated manganese compound according to example two of the present invention.
Detailed Description
The preparation method of the four-coordination manganese compound comprises the following steps:
first step, preparation: according to a molar ratio of 1: (3-3.5): (3-3.5): (3-6) taking the raw materials A, N-butyllithium (N-BuLi), N, N, N ', N' -Tetramethylethylenediamine (TMEDA) and diphenyl phosphorus chloride (Ph)2PCl) for standby;
step two, lithiation reaction: uniformly mixing the raw material A and N, N, N ', N' -tetramethylethylenediamine to obtain a mixed system, dissolving the mixed system in 30-60 mL of a dry solvent system, dropwise adding N-butyllithium into the mixed system at the temperature of-78 +/-5 ℃ under the protection of nitrogen to perform lithiation reaction, and reacting at normal temperature for 12-18 hours to obtain a mixture B; the dry solvent system is an ether solvent system.
Step three, phosphating reaction: dropwise adding diphenylphosphine chloride into the mixture B for carrying out a phosphating reaction at the temperature of 78 +/-5 ℃ under the protection of nitrogen, reacting for 12-18 hours at normal temperature, extracting the obtained phosphating reaction product with water and dichloromethane, taking an organic layer, and extracting the organic layer with anhydrous NaSO4Drying and spin-drying to obtain the solid diphenylphosphine compound.
Step four, oxidation reaction: dissolving a diphenylphosphine compound in a dichloromethane system of 15-50 mL, and adding 3-15 mL of 30% H2O2And stirring and reacting for 4-10 hours at room temperature to obtain the diphenylphosphine oxide compound.
The fifth step is to react the diphenylphosphine oxide with a manganese dihalide (MnY)2) According to a molar ratio of 1: (1-2) dissolving the mixture in 15-50 mL of dichloromethane or ethanol solvent system, reacting for 2-6 hours at normal temperature or 70 +/-5 ℃, performing suction filtration, washing with dichloromethane, and drying to obtain the green light-emitting four-coordinate manganese compound.
The synthetic method of the invention has the following route:
wherein X is O or S, Y is F, Cl, Br, I or SCN, R is CnH2n+1N is an integer of 0 to 18; r' is H or C (CH)3)3。
Wherein the chemical formula of the raw material A is
X is O, S and R' is H, C (CH)3)3R is CnH2n+1And n is an integer of 0 to 18.
When the chemical formula of the raw material A is
The synthetic route is as follows:
x is O or S.
The structural general formula of the four-coordination manganese compound is as follows:
wherein X is O, S, Y is F, Cl, Br, I or SCN, R' is H, C (CH)3)3R is CnH2n+1And n is an integer of 0 to 18.
Example one
When X is O and Y is Br, the raw material A is dibenzofuran, and a four-coordination manganese compound DBFDPO-MnBr2The synthetic route of (A) is as follows:
wherein, the preparation method of the diphenyl phosphine oxide DBFDPO comprises the following steps:
at-78 ℃ in a dry ether solvent (50mL) system under the protection of nitrogen, dropwise adding N-butyllithium (2.4M in an N-hexane solvent, namely the concentration of the N-butyllithium in the N-hexane solution is 2.4 mol/L; 12.5mL,30mmol) into a mixed system consisting of dibenzofuran (1.68g,10mmol) and N, N, N ', N' -tetramethylethylenediamine (4.6mL,30mmol), removing the ice bath device after all the N-butyllithium is added, moving the reaction system to room temperature, and sealing for reactionAfter 12 hours, the mixed system was cooled again to-78 ℃, and under nitrogen protection, a diphenyl phosphorus chloride compound (5.9mL,33mmol) was added dropwise, and then the ice bath apparatus was removed, followed by reaction at room temperature for 12 hours. After completion of the reaction, water (10mL) was added to the reaction system to quench. Extracting with water and dichloromethane, collecting organic layer, and extracting with anhydrous NaSO4Drying and spin-drying to obtain the diphenylphosphine compound. The diphenylphosphine compound was dissolved in a dichloromethane system (20mL), and then 30% H was added2O2(3mL), the reaction was stirred at room temperature for 4 hours, then saturated NaHSO3Extracting the solution with dichloromethane, collecting organic layer, and extracting with anhydrous NaSO4Drying, spin-drying, and separating and purifying to obtain the corresponding diphenylphosphine oxide DBFDPO with a yield of 53%. The structural characterization data of the diphenylphosphine oxide DBFDPO include a hydrogen spectrum:1H NMR(400MHz,CDCl3TMS): δ 8.185(d, J7.6 Hz,2H),7.782(dd, J7.4, 13Hz,2H), 7.691-7.590 (m,8H), 7.520-7.432 (m,6H), 7.401-7.307 ppm (m, 8H); the mass spectrum data is: MALDI-TOF M/z (%) < 591(100) < M + Na]+；C36H26O3P2The calculated value of the element analysis of (1) is C76.05, H4.61, O8.44; measured values of C76.10, H4.61, O8.53.
Four-coordinate manganese compound DBFDPO-MnBr2The preparation method comprises the following steps:
to a dichloromethane solvent system (20mL) was added equimolar amounts of DBFDPO (568mg,1.0mmol) and MnBr2·4H2And O (286.8mg,1.0mmol), reacting the two compounds at room temperature for 2 hours, after the reaction is finished, carrying out suction filtration on the mixed system, washing the product with dichloromethane, and drying to obtain the green light-emitting four-coordination manganese compound with the yield of 85%. The structural characterization data of the four-coordinate manganese compound comprises the following mass spectrum: MALDI-TOF M/z (%) [ M-Br ] 703(100)]+。
Example two
When X is O and Y is Cl, the four-coordinated manganese compound DBFDPO-MnCl2The synthetic route of (A) is as follows:
the preparation method of diphenylphosphine oxide DBFDPO in this example is the same as that of example one.
In this example, a four-coordinated manganese compound DBFDPO-MnCl was used2The preparation method comprises the following steps:
to an ethanol solvent system (20mL) was added equal molar amounts of DBFDPO (568mg,1.0mmol) and MnCl2·4H2And O (197.8mg,1.0mmol) and the two react at 70 ℃ for 6 hours, after the reaction is finished, the mixed system is filtered, the product is washed by dichloromethane, and the product is dried to obtain the green light-emitting four-coordination manganese compound, wherein the yield is 70%. The structural characterization data of the four-coordinate manganese compound comprises the following mass spectrum: MALDI-TOF M/z (%) [ 658(100) [ [ M-Cl ]]+。
Four-coordinate manganese compound DBFDPO-MnBr2With DBFDPO-MnCl2The photophysical properties of (a) are characterized as follows:
(1) the compounds DBFDPO, DBFDPO-MnBr prepared in the above examples I and II were tested on a UV-1700Shimadzu UV-Vis absorption spectrometer2And DBFDPO-MnCl2The absorption spectrum of (2) is shown in FIG. 1. From the absorption spectrum, it is known that the absorption of the manganese compound in the solution and thin film state is mainly due to the absorption of its chelating organic ligand DBFDPO.
(2) The compound DBFDPO-MnBr prepared in the first and second examples was tested on an Edinburgh FL 920 fluorescence spectrometer2And DBFDPO-MnCl2Solid state emission spectrum and excitation spectrum of (a), as shown in fig. 2. The data in the emission spectrum of the compound show that the compound DBFDPO-MnBr is at the excitation wavelength of 320nm2Has a maximum emission wavelength of 540 nm; compound DBFDPO-MnCl2Has a maximum emission wavelength of 520nm, and the manganese compounds are bothStronger green emission is achieved.
(3) The compound DBFDPO-MnBr prepared in the first and second examples was tested on an Edinburgh FL 920 fluorescence spectrometer2And DBFDPO-MnCl2As shown in fig. 3 and 4. The data in the figure are fitted to obtain the compound DBFDPO-MnBr2Has a solid state luminescence lifetime of 1.0ms, and is a compound DBFDPO-MnCl2The solid state luminescence lifetime of (a) is 5.2ms, which is the longest lifetime of the luminescent manganese compounds found to date.
EXAMPLE III
The embodiment provides application of a novel four-coordination manganese compound with a bipolar structure as a luminescent material.
Manganese complex DBFDPO-MnBr2The fluorescent material has strong green phosphorescent emission in a solid state, has a maximum emission wavelength of 540nm, shows green emission, has a lifetime of 1.0ms, and belongs to phosphorescent emission. The manganese compound can be used as a luminescent material or a luminescent doping body and is used in Organic Light Emitting Diodes (OLEDs).
In addition, the four-coordinate manganese compound with other structure is structurally and synthetically combined with DBFDPO-MnBr2The material properties of the materials are similar, so that the material can also generate DBFDPO-MnBr in the aspect of luminescent materials2Similar effects.
Example four
The embodiment provides a novel four-coordination manganese compound with a bipolar structure as an electrophosphorescent material applied to preparation of organic electrophosphorescent devices (PhOLEDs) by an evaporation method.
The structure of the organic light emitting diode selected may be various structures known in the art. Preferably, the organic light emitting diode includes an anode layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode layer. Prepared phosphorescent four-coordination manganese compound DBFDPO-MnBr2The material is a luminescent material, and is doped into a TcTa:2, 6-DCZPyP mixed main body material by the mass percentage of 5-20% to be used as a luminescent layer to prepare an organic light-emitting diode, wherein the structure of the organic light-emitting diode is as follows: ITO/PEDOT PSS (50nm)/EMLTmPyPb (60nm)/LiF (1nm)/Al (100 nm). Wherein EML is a phosphorescence four-coordination manganese compound prepared by TcTa 2,6-DCZPPY (2:8) + 5-20%.
The preparation method of the organic light-emitting diode comprises the following steps of firstly cleaning an ITO substrate by using deionized water, acetone and isopropanol respectively, then treating for 15 minutes by using UV-ozone, spin-coating filtered PEDOT (PSS) aqueous solution on the ITO substrate on a spin coating instrument at the rotating speed of 3000 rpm, drying for 20 minutes at the temperature of 120 ℃ to obtain a PEDOT (PSS) film with the thickness of 50nm, wherein the PEDOT/PSS film is used as a hole injection layer/hole transport layer, and then utilizing vacuum evaporation equipment to ensure that the vacuum degree is not lower than 4 × 10-4Uniformly mixing TcTa:2, 6-DCZPyP (2:8) and 5-20% of prepared phosphorescent tetradentate manganese compound in a Pa vacuum cavity, and uniformly evaporating the mixture onto a PEDOT: PSS film to form a light-emitting layer with the thickness of 50 nm; subsequently, a TmPyPb electron transport layer with the thickness of 60nm, a LiF electron injection layer with the thickness of 1nm and Al with the thickness of 100nm are sequentially evaporated to be used as a cathode of the device.
The four-coordinate manganese compound with other structures is structurally and synthetically prepared from DBFDPO-MnBr2The material properties are similar due to the common property, so that the material can also generate DBFDPO-MnBr in the aspect of electrophosphorescent material2Similar effects.
EXAMPLE five
The embodiment provides a novel four-coordinate manganese compound with a bipolar structure as an organic storage material applied to preparation of a storage device.
Prepared phosphorescent four-coordination manganese compound DBFDPO-MnBr2The organic resistive random access memory is prepared as an organic resistive random access memory layer material, and the structure of the device is as follows: ITO/X/Al (100 nm).
The preparation method of the organic resistive random access memory comprises the following steps of firstly respectively cleaning an ITO substrate by deionized water, acetone and isopropanol, then treating for 15 minutes by adopting UV-ozone, and then utilizing vacuum evaporation equipment to ensure that the vacuum degree is not lower than 4 × 10-4Evaporating a manganese compound onto the ITO substrate in a vacuum cavity of Pa to form a resistance change storage layer with the thickness of 100 nm; and finally, evaporating Al with the thickness of 100nm on the storage layer to be used as a cathode of the device.
The four-coordinate manganese compound with other structures is structurally and synthetically prepared from DBFDPO-MnBr2The common property exists, the material properties are similar, and therefore, the organic memory material can also generate DBFDPO-MnBr2Similar effects.
In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (8)
1. A four-coordinate manganese compound having a bipolar structure, wherein the four-coordinate manganese compound has a general structural formula as follows:
wherein X is O or S; y is F, Cl, Br, I or SCN.
2. The method for producing a four-coordinate manganese compound having a bipolar structure according to claim 1, comprising the steps of:
step one, mixing the raw materials in a molar ratio of 1: 3-3.5: 3-3.5: 3-6 taking the raw materials A, N-butyllithium, N, N, N ', N' -tetramethylethylenediamine and diphenylphosphoryl chloride for later use; the raw material A is a dibenzo compound, and the chemical formula of the dibenzo compound is
Step two, uniformly mixing the raw material A and N, N, N ', N' -tetramethylethylenediamine to obtain a mixed system, dissolving the mixed system in a dry solvent system, dropwise adding N-butyllithium into the mixed system at the temperature of minus 78 +/-5 ℃ under the protection of nitrogen to perform lithiation reaction, and reacting at normal temperature for 12-18 hours to obtain a mixture B;
thirdly, dropwise adding diphenylphosphine chloride into the mixture B for a phosphating reaction at the temperature of 78 +/-5 ℃ under the protection of nitrogen, and reacting for 12-18 hours at normal temperature to obtain a diphenylphosphine compound;
fourthly, dissolving the diphenylphosphine compound in a dichloromethane system, and then adding 3-15 mL of 30% H by mass fraction2O2Stirring and reacting for 4-10 hours at room temperature to obtain the diphenyl phosphine oxide compound, wherein the chemical formula of the diphenyl phosphine oxide compound is shown in the specification
Fifthly, mixing the diphenyl phosphine oxide compound and the manganese dihalide according to a molar ratio of 1: 1-2, dissolving in a dichloromethane or ethanol solvent system, reacting for 2-6 hours at normal temperature or 70 +/-5 ℃, and performing suction filtration, washing and drying to obtain the tetra-coordinated manganese compound.
3. The method according to claim 2, wherein the tetradentate manganese compound has a chemical formula of
Wherein X is O or S, and Y is F, Cl, Br, I or SCN.
4. The method for preparing a four-coordinate manganese compound with a bipolar structure according to claim 2, wherein in the second step, the dry solvent system is an ether solvent system, and the amount of the ether solvent system used in the reaction process is 30-60 mL; in the fourth step, the reaction dosage of a dichloromethane system is 15-50 mL; in the fifth step, the reaction dosage of the dichloromethane solvent system is 15-50 mL, and the reaction dosage of the ethanol solvent system is 15-50 mL.
5. The method according to claim 2, wherein the organic layer is obtained by extracting the product of the phosphating reaction with water and dichloromethane, and the organic layer is anhydrous NaSO4Drying to obtain solid diphenylphosphineA kind of compound is provided.
6. Use of a four-coordinate manganese compound having a bipolar structure according to claim 1, wherein the four-coordinate manganese compound is used as a light-emitting material.
7. The use of the four-coordinate manganese compound with a bipolar structure of claim 6, wherein the four-coordinate manganese compound is used as an electrophosphorescent material in an organic electrophosphorescent device; the organic electrophosphorescent device comprises a first electrode, a second electrode and at least one organic functional layer formed between the first electrode and the second electrode, wherein the organic functional layer contains a four-coordinate manganese compound.
8. Use of a tetra-coordinated manganese compound having a bipolar structure according to claim 6, wherein said tetra-coordinated manganese compound is used as an organic memory material.
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