CN112694500B - Novel phosphine-oxygen bidentate neutral manganese complex and preparation method and application thereof - Google Patents
Novel phosphine-oxygen bidentate neutral manganese complex and preparation method and application thereof Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 60
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- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 57
- 230000007935 neutral effect Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- 238000010668 complexation reaction Methods 0.000 title description 2
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- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 19
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- 150000001875 compounds Chemical class 0.000 claims description 4
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- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims 1
- 230000005622 photoelectricity Effects 0.000 claims 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 description 7
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- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 3
- 238000005424 photoluminescence Methods 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
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- 238000007650 screen-printing Methods 0.000 description 2
- -1 (dicyclohexylphosphine) -dibenzopyran Chemical class 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- CURDFNDNSXWXAD-UHFFFAOYSA-N [O-2].P.[Mn+2] Chemical compound [O-2].P.[Mn+2] CURDFNDNSXWXAD-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
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- 239000013557 residual solvent Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000000904 thermoluminescence Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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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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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
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Abstract
The invention provides a novel phosphine-oxygen bidentate neutral manganese complex and a preparation method and application thereof, wherein a luminescent manganese complex is formed through the action of a bidentate phosphine-oxygen bond and manganese metal, two benzene rings on P can be replaced by cyclohexyl to form another novel structure through the ligand, and the structures can optically regulate and control the manganese metal complex by adjusting a ligand field and a ligand proportion; because of the advantages of low price, low cost, simple synthesis and the like of the metal manganese, the neutral manganese complex has wide application and can be applied to the fields of anti-counterfeiting printing, illumination display and the like.
Description
Technical Field
The invention belongs to the technical field of photoluminescence materials, and particularly relates to a novel phosphine oxide bidentate neutral manganese complex and a preparation method thereof, which can be applied to the fields of printing, information anti-counterfeiting, photoelectric display, biosensing and imaging.
Background
The luminescent material is widely applied to the fields of illumination, photoelectric display, biological imaging and the like due to the characteristics of the luminescent material. In recent decades, the phosphorescent metal complex has attracted much attention due to its low cost and excellent optical properties. In most cases, the phosphorescent metal complexes include noble metals such as Ir (III), Pt (II), Re (I), Ag (I), Au (I), Mn (II), etc., and the phosphorescent emission of these noble metal complexes is mainly due to charge transfer between the metal ions and the ligands. The iridium complex has high-efficiency light emission and high stability, is widely applied to the fields of illumination and display, but cannot meet the illumination requirement in the field of life due to high production cost; meanwhile, the toxicity of the platinum complex is relatively high. In recent years, research shows that: among the numerous luminescent metal complexes, complexes based on the metal mn (ii) are receiving increasing attention due to their unique superior properties of light, friction, electroluminescence, thermoluminescence, simplicity of preparation, and abundance. The metal manganese complex generally shows phosphorescence emission at room temperature, the fluorescence emission with short service life is mainly related to d-d orbital transition of the center of metal Mn (II), and the phosphorescence emission of the manganese complex is highly sensitive to a ligand field and a coordination environment around manganese, so that the metal manganese complex generally shows red light or green light emission and shows green light when the metal manganese is in a four-coordination environment; when the coordination number is six, an octahedron is formed with the manganese metal center to display red light or orange light, and even under certain conditions, penta-coordination or hepta-coordination is generated. Due to the difference of coordination numbers and coordination environments, the metal manganese complex can emit light with different colors. Therefore, the regulation and control of light with different colors can be realized by changing the coordination number around the metal manganese and the ligand field environment.
Because the existing bidentate phosphine manganese oxide complex has less research and single color, it is necessary to design a ligand and realize color diversification by regulating and controlling the proportion.
Disclosure of Invention
The invention aims to regulate and control the coordination number and the coordination environment around metal Mn (II) to form a novel phosphine-oxygen bidentate neutral manganese complex so as to realize light conversion of different colors.
The invention provides a novel phosphine-oxygen bidentate neutral manganese complex which is characterized in that the structural formula of the manganese complex is one of the following structural formulas and is divided into three general structural formulas, namely a general structural formula I, a general structural formula II and a general structural formula III:
wherein, X is Br, Cl or I.
Further, the synthetic routes of the compounds represented by general structural formulas I and II are as follows:
further, the synthetic route of the compound represented by the general structural formula III is as follows:
furthermore, when heavy atoms Br participate in the coordination around manganese, the photophysical properties are better than those of other halogen atoms; the structural formula of the manganese complex is shown as the following structure, and the manganese complex is marked as a complex Cp 1;
furthermore, the coordination number around the manganese is regulated by a regulating means, the coordination number and the proportion of the ligands are mainly regulated, and the manganese complex with the following structural formula is synthesized and is marked as a complex Cp 2:
furthermore, the coordination number around the manganese is regulated by a regulating means, the coordination number and the proportion of the ligands are mainly regulated, and the manganese complex with the following structural formula is synthesized and is marked as a complex Cp 3:
the application of the novel phosphine oxide bidentate manganese complex can be specifically applied to:
1. the manganese complex solution can be used as ink and applied to the fields of printing and printing;
2. the manganese complex can be made into a film, is small and can be widely applied to the photoelectric field;
3. the manganese complex can be made into fluorescent powder to make LED small bulbs with different colors;
4. the manganese complex can be applied to the fields of photoelectric display, biological imaging and sensing, X-ray detection and information recording.
The novel phosphine oxide bidentate neutral manganese complex provided by the invention has the following advantages:
1. excellent photophysical properties and high thermal stability, such as: green light and yellow light are emitted under the solid state, and the light quantum yield is higher;
2. the neutral phosphine oxide bidentate manganese complex designed by the invention can realize the regulation and control of the light emitting color by changing the ligand field.
The preparation method of the novel phosphine oxide bidentate neutral manganese complex provided by the invention has the following advantages:
simple experimental synthesis, low cost and low toxicity.
Drawings
FIG. 1: normalized solid state emission spectra of neutral phosphine oxide bidentate manganese complexes Cp1, Cp2 described in inventive examples 1 and 2;
FIG. 2: the solid-state photoluminescence lifetime decay curves of the neutral phosphine oxide bidentate manganese complexes Cp1 and Cp2 disclosed in the embodiment 1 and the embodiment 2 of the invention;
FIG. 3: CIE 1931 chromaticity diagram of neutral phosphine oxide bidentate manganese complexes Cp1 and Cp2 described in inventive examples 1 and 2;
FIG. 4: application of the neutral phosphine-oxygen bidentate manganese complexes Cp1, Cp2 described in inventive examples 1 and 2 as inks for screen printing.
Detailed Description
Example 1: synthesis of Phosphinoxy bidentate manganese Complex Cp1
The specific synthesis method comprises the following steps:
synthesis of mono, 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene (ligand L1)
Step a: putting the raw materials into a reaction bottle, vacuumizing, and blowing nitrogen;
step b: injecting ultra-dry tetrahydrofuran, stirring and fully dissolving;
step c: cooling to-78 deg.C in a low-temperature tank containing dry ice and acetone, adding butyl lithium, and lithiating.
Step d: injecting corresponding diphenyl phosphine chloride according to the equivalent ratio of 1:2.5 of diphenyl phosphine chloride to carry out phosphating reaction, removing a low-temperature tank after adding diphenyl phosphine chloride to react, slowly returning to room temperature, stirring for reaction, distilling under reduced pressure to remove a solvent, extracting with dichloromethane and water to obtain an organic layer, removing water by using anhydrous sodium sulfate, and suspending to dry for purification.
Step e: using petroleum ether and dichloromethane as eluent, and carrying out column chromatography purification treatment to obtain a phosphorized product, namely white powder.
Synthesis of di, ligand DDXPO
1g of ligand L1(4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene) was weighed into a 250mL reaction flask containing magnetons, and 50mLCH was injected2Cl2Stirring to dissolve it completely. And then adding hydrogen peroxide with the mass fraction of 30% for oxidation reaction, and oxidizing for 2 h. And (3) after complete oxidation, carrying out extraction treatment, separating a dichloro reaction solution from water, collecting an organic layer, carrying out dehydration treatment by using anhydrous sodium sulfate, and carrying out reduced pressure distillation to remove residual solvent to obtain a white powder product, wherein the yield is 85%. C39H32O3P2The theoretical molecular weight of (1) is 610.19, and the actually tested mass spectrum molecular weight is: 633.28[ M + Na ]]+。
Structural characterization data for ligand DDXPO:
1H NMR(400MHz,CDCl3):δ7.59(d,J＝6.8Hz,2H),7.46-7.41(m,12H),7.35-7.31(m,8H),6.97(t,J＝9.0Hz,2H),6.83-6.77(m,2H),1.69(s,6H)。
synthesis of tri-phosphine-oxygen bidentate manganese complex Cp1
Weighing 1g of the ligand DDXPO in a single-mouth eggplant-shaped bottle, and adding 25mLCH2Cl2Fully dissolving, adding corresponding mixture ratio (DDXPO: MnBr) after complete dissolution2·4H2O1: 1), stirring for 12h, filtering, and vacuum dryingThe green-emitting manganese complex Cp1 was obtained in 80% yield. Cp1 (C)39H32Br2MnO3P2) Mass spectrometry molecular weight is 744.15[ M-Br ]]+。
Example 2: synthesis of Phosphinoxy bidentate manganese Complex Cp2
The synthesis of the complex Cp2 was carried out in the same manner as in the basic procedure of Cp1, i.e.in the same manner as in step one and step two, except that Cp2 was obtained by controlling the coordination number.
Example 3: synthesis of phosphine oxide bidentate manganese complex Cp 3:
synthesis of the Complex Cp 3: wherein ligand L2(4, 5-bis (dicyclohexylphosphine) -dibenzopyran derivative) can be directly purchased and then directly coordinated with manganese bromide, and the coordination synthesis method is the same as the synthesis method of step three in example 1, so that the green-light manganese complex can be obtained.
Test example 1: normalized solid state emission spectra of the novel phosphine-oxide bidentate neutral manganese complexes Cp1, Cp 2;
according to FIG. 1, it was found that the emission characteristic peaks of complexes Cp1 and Cp2, at the 530nm and 583nm positions, respectively, correspond to the characteristic emission of green and yellow light.
Test example 2: solid state photoluminescence lifetime decay curves for the novel phosphine-oxide bidentate neutral manganese complexes Cp1, Cp 2;
as shown in FIG. 2, it was found that the complex Cp2 has a longer lifetime by about 5 times than Cp1 and thus has a longer lifetime.
Test example 3: according to fig. 3, Cp1 is in the green region, Cp2 is in the yellow region, and the (x, y) coordinates are (0.295,0.654), (0.530,0.467), respectively.
Application example 1: application of novel phosphine-oxygen bidentate neutral manganese complex as ink for silk-screen printing
As shown in fig. 4, the manganese complex is dissolved in ethanol and then doped with polyethylene glycol 10000(PEG) to prepare ink, and the screen is used for printing the mold, so that the effect is remarkable. The printed pattern does not emit light under sunlight, only shows white PEG film, and emits the color of the complex under ultraviolet irradiation, and has wide application and profound research significance.
Application example 2: in the research process of the manganese complex, the manganese complex can be dissolved and spin-coated to be made into a film; based on the method, the film is miniaturized and can be applied to various fields of photoelectric luminescent materials.
Application example 3: the manganese complex can be prepared into a fluorescent powder material in a grinding and doping mode, and can be applied to the field of illumination and display.
Application example 4: the manganese complex can be used as a luminescent material due to the advantages of high stability, high-efficiency luminescence, simple synthesis and the like, and can be applied to the fields of biological imaging, information recording, detection, imaging and the like.
Claims (9)
1. A phosphine oxide bidentate neutral manganese complex is characterized in that the structural formula of the manganese complex is one of the following structural formulas:
wherein, X is Br, Cl and I.
2. The preparation method of the phosphine oxide bidentate neutral manganese complex as claimed in claim 1, wherein the synthetic routes of the compounds represented by the structural formulas I and II are as follows:
3. the preparation method of the phosphine oxide bidentate neutral manganese complex as claimed in claim 1, wherein the synthetic route of the compound represented by the general structural formula III is as follows:
4. the preparation method of the phosphine oxide bidentate neutral manganese complex as claimed in claim 2, wherein the manganese complex has a structural formula:
5. the preparation method of the phosphine oxide bidentate neutral manganese complex as claimed in claim 2, wherein the manganese complex has a structural formula:
6. the preparation method of the phosphine oxide bidentate neutral manganese complex as claimed in claim 3, wherein the manganese complex has a structural formula:
7. the use of a phosphino bidentate neutral manganese complex as claimed in claim 1, characterized in that the manganese complex solution is used in the printing and printing field as an ink.
8. The application of the phosphine oxide bidentate neutral manganese complex as claimed in claim 1, characterized in that the manganese complex is applied in the field of photoelectricity.
9. The phosphine-oxide bidentate neutral manganese complex as set forth in claim 1, as a luminescent material, and the manganese complex is applied to the fields of photoelectric display, biological imaging and sensing.
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|---|---|---|---|---|
| FR2932181A1 (en) * | 2008-06-05 | 2009-12-11 | Rhodia Operations | Reduction of a functional group containing phosphorus atom in a substrate, comprises placing the substrate in the presence of a siloxane type compound associated with a base catalyst of a metal element |
| CN108250246A (en) * | 2018-03-16 | 2018-07-06 | 南京邮电大学 | Four-coordination manganese compound with bipolar structure and its preparation method and application |
| CN111747987A (en) * | 2020-07-30 | 2020-10-09 | 南京邮电大学 | Novel neutral monodentate chelated manganese complex and preparation method and application thereof |
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2020
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2932181A1 (en) * | 2008-06-05 | 2009-12-11 | Rhodia Operations | Reduction of a functional group containing phosphorus atom in a substrate, comprises placing the substrate in the presence of a siloxane type compound associated with a base catalyst of a metal element |
| CN108250246A (en) * | 2018-03-16 | 2018-07-06 | 南京邮电大学 | Four-coordination manganese compound with bipolar structure and its preparation method and application |
| CN111747987A (en) * | 2020-07-30 | 2020-10-09 | 南京邮电大学 | Novel neutral monodentate chelated manganese complex and preparation method and application thereof |
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