CN112500436B - Method for synthesizing platinum carbene phosphorescent material metallization - Google Patents
Method for synthesizing platinum carbene phosphorescent material metallization Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 71
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 32
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 29
- 238000001465 metallisation Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title claims description 5
- 239000002904 solvent Substances 0.000 claims abstract description 52
- 239000003446 ligand Substances 0.000 claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000741 silica gel Substances 0.000 claims abstract description 27
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 27
- 238000009835 boiling Methods 0.000 claims abstract description 17
- 238000001308 synthesis method Methods 0.000 claims abstract description 14
- 239000002585 base Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 98
- 229910052757 nitrogen Inorganic materials 0.000 claims description 50
- VVAOPCKKNIUEEU-PHFPKPIQSA-L dichloro(cycloocta-1,5-diene)platinum(ii) Chemical compound Cl[Pt]Cl.C\1C\C=C/CC\C=C/1 VVAOPCKKNIUEEU-PHFPKPIQSA-L 0.000 claims description 28
- -1 hydroxy, mercapto, cyano, amino Chemical group 0.000 claims description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- CHOAEQJHUDQYIJ-UHFFFAOYSA-L [Cl-].[Cl-].[Pt++].C1=CC=CC=CC=C1 Chemical compound [Cl-].[Cl-].[Pt++].C1=CC=CC=CC=C1 CHOAEQJHUDQYIJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 3
- 229910052805 deuterium Inorganic materials 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
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- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 2
- 125000004986 diarylamino group Chemical group 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
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- 239000012043 crude product Substances 0.000 description 47
- 239000000047 product Substances 0.000 description 29
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 25
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- 239000007787 solid Substances 0.000 description 24
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 23
- 239000001632 sodium acetate Substances 0.000 description 23
- 235000017281 sodium acetate Nutrition 0.000 description 23
- 238000004821 distillation Methods 0.000 description 21
- 239000003480 eluent Substances 0.000 description 21
- 238000012512 characterization method Methods 0.000 description 17
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
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- 239000002184 metal Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
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- 239000013557 residual solvent Substances 0.000 description 4
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 3
- BDLXTDLGTWNUFM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethanol Chemical compound CC(C)(C)OCCO BDLXTDLGTWNUFM-UHFFFAOYSA-N 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
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- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
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- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
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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
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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Abstract
The invention discloses a synthesis method of platinum carbene phosphorescence material metallization, which adopts molecules with boiling point of 120-250 ℃ and bidentate or multidentate coordination capability as solvent, under the protection of alkali and inert gas, the molar ratio of a tridentate or tetradentate ligand containing carbene to platinum metal salt is 0.94-0.97:1, adding the raw materials into a solvent, reacting for 0.5-5.0 days at the temperature of 95-130 ℃, distilling under reduced pressure to remove the solvent, and separating and purifying by using a silica gel chromatographic column to obtain a metallized platinum carbene phosphorescent material; the volume mol ratio of the solvent to the tridentate or tetradentate ligand containing the carbene is 13-108:1, the ligand to base equivalent ratio is 1:3. The method eliminates the explosion risk caused by high pressure in the prior method, and simultaneously improves the yield of the reaction.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a synthesis method for metallization of a platinum carbene phosphorescent material.
Background
Organic Light Emitting Diodes (OLEDs) are also called Organic Light-Emitting devices (Organic Light-Emitting devices) or Organic Electroluminescent devices (Organic Electroluminescent devices). The organic electroluminescence is a luminescence phenomenon that under the action of a forward bias electric field, an organic small molecule, a metal organic complex molecule or a polymer molecule luminescent material directly converts electric energy into light energy. The OLED is self-luminous, does not need a backlight source and saves energy; the LED display also has the characteristics of high response speed, low driving voltage, high luminous efficiency and resolution, wide visual angle, high contrast and the like; in addition, the substrate can be made of cheap glass, metal or even flexible plastic, so that the substrate has the advantages of low cost, simple production process, large-area production and the like, becomes a new generation of full-color display and illumination technology, has wide and huge application prospect in the fields of mobile phones, computers, televisions, digital cameras, GPS, bendable and foldable electronic products and illumination, and is widely valued by the academic and industrial fields.
Phosphorescent light emitting materials have been the core of the development in the field of OLEDs. The carbene and the azacarbene are strong sigma donors and can be used as weak pi acceptors, so that the carbene and the azacarbene can form stable metal complex phosphorescent materials with a plurality of transition metal ions such as Pt (II), pd (II), ir (III), cu (II), au (I), au (III), ag (I) and the like. Meanwhile, the phosphorescent materials based on the tetradentate cyclometalated platinum complex containing the carbene ligand have wide application in blue light, deep blue light and single-molecule doped white OLEDs due to the characteristics of high quantum efficiency, narrow emission spectrum and the like, and have attracted wide attention in academic and industrial circles (angelw.chem.int.ed.2013, 52,6753, adv.mater.2014,26,2931 adv.mater.2014,26,7116 adv.optical mater.2015,3,390 inorg.chem.2017,56, 8244. However, in the synthesis of the cyclometalated platinum complex phosphorescent material containing the carbene ligand, particularly the final key step, namely the metallization of the ligand, has been a problem. Firstly, the reaction yield is low, generally about 20%, which causes large consumption of precious ligands and precious metal salts and high cost; secondly, the reaction needs a high-temperature tube-sealing reaction system, and the explosion risk is! After a large amount of experimental exploration and optimization, researchers find that Tetrahydrofuran (THF) is an excellent solvent for ligand metallation reaction, and is also a solvent used in the currently reported synthetic methods, and target material molecules can be obtained by heating reaction at 120 ℃. But tetrahydrofuran has a low boiling point (66 ℃ C.), and therefore needs to be heated to 120 ℃ under sealed conditions, which results in a large increase in the pressure inside the reaction system, with the risk of explosion! The occurrence of reaction explosion accidents not only can cause reaction failure and waste of precious raw materials, but also can cause great threat to the personal safety of experimenters. Therefore, how to improve the yield of the carbene ligand metallation, especially eliminating the risk of reaction explosion, is an important problem to be solved urgently in the material synthesis.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a synthesis method for metallization of a platinum carbene phosphorescent material, which eliminates the explosion risk caused by high pressure in the prior art and simultaneously improves the yield of the reaction.
In order to achieve the purpose, the invention adopts the technical scheme that: a synthesis method of platinum carbene phosphorescent material metallization adopts molecules with boiling point of 120-250 ℃ and bidentate or multidentate coordination capability as solvents, under the protection of alkali and inert gas, a tridentate or tetradentate ligand containing carbene and platinum metal salt are mixed according to the molar ratio of 0.94-0.97:1, adding the raw materials into a solvent, reacting for 0.5-5.0 days at the temperature of 95-130 ℃, distilling under reduced pressure to remove the solvent, and separating and purifying by using a silica gel chromatographic column to obtain a metallized platinum carbene phosphorescent material; the volume mol ratio of the solvent to the tridentate or tetradentate ligand containing the carbene is 13-108:1, the ligand to base equivalent ratio is 1:3.
Further, the general formula of the solvent is:
wherein R is 1 And R 2 Hydrogen, deuterium or C1-C4 alkyl.
Further, the inert gas is argon or nitrogen.
Further, the base is one or more of alkali metal acetate, alkali metal carbonate, alkali metal bicarbonate, alkali metal phosphate, alkali metal acid phosphate and alkali metal alcoholate which are mixed according to any proportion.
Further, the platinum metal salt is potassium tetrachloroplatinate, sodium tetrachloroplatinate, platinum dichloride, (1,5-cyclooctadiene) platinum dichloride or (1,3,5,7-cyclooctatetraene) platinum dichloride.
Compared with the prior art, the invention has the beneficial effects that: the generation of the target product in the synthesis method needs to be carried out by the processes of generating the carbene ligand by hydrogen abstraction of the carbene precursor quaternary ammonium salt under the action of alkali, ligand exchange of the carbene ligand and metal salt, formation of metal-carbon bond in molecules and the like. Wherein, the reaction temperature and alkali have certain influence on the synthesis yield of the target product, and the alkali also plays a role in neutralizing the hydrogen halide generated by the reaction; the formation of intramolecular metal-carbon bonds requires a suitable temperature to be able to take place successfully. Further, the solvent has a significant influence on the yield of the target product of the cyclometal complex, mainly because solvent molecules with bidentate or multidentate coordination ability can stabilize the reaction intermediates. In addition, under the same reaction conditions, the stability of different ligand structures also has influence on the yield, and the reaction can be carried out in a reaction tube or a conventional reaction bottle with a condensing device without tube sealing; even if a tube sealing is used, the pressure inside the reaction system can be greatly reduced due to the high boiling point of the reaction solvent, and the risk of explosion is avoided. The method can greatly improve the previous harsh reaction conditions, greatly reduce the risk of metallization reaction, and has important application in the synthesis of related carbene-based cyclometalated platinum phosphorescent materials. In addition, the solvents developed in the process of the invention all have very high flash points, which are much safer than the tetrahydrofuran (flash point: -14 ℃) used traditionally.
Drawings
FIG. 1 is a schematic diagram of a reaction tube device of the synthesis method of platinum carbene phosphorescent material metallization of the invention;
FIG. 2 is a thermogravimetric plot of PtON5-mm with a thermal decomposition temperature above 400 ℃;
FIG. 3 is a graph of the emission spectra of PtON5-mm in 2-methyltetrahydrofuran at 77K and in dichloromethane at room temperature; wherein 2-MeTHF is 2-methyltetrahydrofuran, DCM is dichloromethane;
FIG. 4 is a graph of the emission spectra of PtON7p-tt in 2-methyltetrahydrofuran at 77K and in dichloromethane at room temperature; wherein 2-MeTHF is 2-methyltetrahydrofuran, DCM is dichloromethane;
FIG. 5 is a graph of the emission spectra of PtON5N-tt in 2-methyltetrahydrofuran at 77K and in dichloromethane at room temperature; wherein 2-MeTHF is 2-methyltetrahydrofuran and DCM is dichloromethane.
Detailed Description
The following examples, which are merely exemplary of the present disclosure and are not intended to be limiting in scope, provide those of ordinary skill in the art with a view to performing and evaluating the metallization operations described herein and the effect of each solvent thereon. Although efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), some errors and deviations should be accounted for. Unless otherwise specified, temperature is in units of ° c or at ambient temperature, and pressure is at or near atmospheric pressure.
FIG. 1 is a schematic view of the reaction tube apparatus of the synthesis method for platinum carbene phosphorescent material metallization according to the present invention, wherein the tube sealing portion higher than the oil bath can function as an air condenser tube, due to the high boiling point of the reaction solvent, the solvent vapor above the reaction mixture can be effectively cooled, the safety of the reaction can be ensured, the volume of the reaction tube can be adjusted according to the scale of the reaction, and a cooling tube is additionally installed. The reaction tube device is not limited thereto, and this is only an example.
The following examples are merely exemplary, ligand reactants, temperature, metallized platinum source, concentration, base, and other process conditions may be varied, and one skilled in the art to which this disclosure pertains may readily select appropriate reactants and conditions for preparation of the desired compound.
Performed on a Varian Liquid State NMR instrument 1 H and 13 c NMR spectrum test. The solvent is CDCl 3 Or DMSO-d 6 . If tetramethylsilane is an internal standard in the solvent, the chemical shift is referred to tetramethylsilane (delta =0.00 ppm); otherwise, if CDCl is used 3 Is a solvent, and is prepared by mixing the components, 1 chemical shifts of H NMR spectra were referenced to residual solvent (δ =7.26 ppm), 13 chemical shifts of the C NMR spectrum are referenced to residual solvent (δ =77.00 ppm); if DMSO-d is used 6 Is a solvent, and is prepared by mixing the components, 1 chemical shift of H NMR spectrum is compared with residual solvent H 2 O(δ＝3.33ppm)， 13 Chemical shift of C NMR spectrum is compared with that of residual solvent DMSO-d 6 (δ =39.52 ppm). The nuclear magnetic data in the examples are explained using the following abbreviations (or combinations thereof) 1 Multiplicity of H NMR: s = singleplex, d = doublet, t = triplet, q = quadruplet, p = quintuple, m = multiplet, br = wide.
Example 1: the platinum (II) complex PtON5N-tt can be synthesized as follows:
to a reaction tube with a magnetically stirred rotor (see FIG. 1) were added sequentially ligand LON5N-tt (1.69g, 2.33mmol,1.0 eq), (1,5-cyclooctadiene) platinum dichloride (915mg, 2.45mmol,1.05 eq) and sodium acetate (573mg, 6.99mmol,3.0 eq), then nitrogen was purged three times and diethylene glycol dimethyl ether (64 mL) was added under nitrogen. Stirring in oil bath at 95-125 deg.C for 3 days, cooling to room temperature, and distilling under reduced pressure to remove solventAnd (5) preparing a crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a lotion: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give the product PtON5N-tt yellow solid 1.21g, 67% yield. 1 H NMR(500MHz,DMSO-d 6 ):δ1.35(s,9H),1.42(s,9H),4.08(s,3H),7.01(d,J＝1.5Hz,1H),7.27-7.31(m,2H),7.40(t,J＝7.5Hz,1H),7.48-7.53(m,2H),7.91(d,J＝8.0Hz,1H),8.09-8.12(m,2H),8.16(d,J＝8.0Hz,1H),8.23(dd,J＝8.0,1.0Hz,1H),8.51(d,J＝2.0Hz,1H),8.59(dd,J＝5.0,1.5Hz,1H),9.49(d,J＝6.5Hz,1H)。 13 C NMR(125MHz,CDCl 3 ):δ29.96,31.69,34.34,34.96,35.45,106.61,107.92,110.73,112.74,113.11,114.08,115.57,116.21,116.42,116.66,117.70,117.87,120.01,122.41,123.67,128.31,129.11,138.81,143.57,144.58,145.93,148.81,148.85,149.35,151.80,154.69,155.41,163.53,194.77。HRMS(ESI):C 38 H 36 N 5 O 195 Pt[M+H] + Calcd 773.2562, found 773.2564.
In addition, it was found by experiment that similar yields to example 1 could be obtained if the reaction of example 1 was carried out at 95-130 ℃ or in a sealed tube.
Example 2: the platinum (II) complex PtON5N-tt can be synthesized by the following route:
to a sealed tube with a magnetically stirred rotor were added sequentially the ligand LON5N-tt (3.40g, 4.68mmol,1.0 equiv), (1,5-cyclooctadiene) platinum dichloride (1.84g, 4.92mmol,1.05 equiv) and sodium acetate (1.15g, 14.04mmol,3.0 equiv), then nitrogen was purged three times and diethylene glycol dimethyl ether (68 mL) was added under nitrogen. Then stirring and reacting for 3 days in an oil bath kettle at the temperature of 100-130 ℃, cooling to room temperature, and removing the solvent by reduced pressure distillation to obtain a crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether to dichloromethane was 10-2:1 to give 2.58g of the product PtON5N-tt yellow solid in 71% yield. 1 H NMR characterization was consistent with example 1.
Example 3: the platinum (II) complex PtON5N-tt can be synthesized by the following route:
to a reaction tube equipped with a magnetically stirred rotor were added sequentially ligand LON5N-tt (100mg, 0.14mmol,1.0 equiv), (1,5-cyclooctadiene) platinum dichloride (54mg, 0.144mmol,1.05 equiv) and sodium acetate (34mg, 0.41mmol,3.0 equiv), then nitrogen was purged three times and diethylene glycol diethyl ether (15 mL) was added under nitrogen. Then stirring and reacting for 3 days in an oil bath kettle at the temperature of 100-130 ℃, cooling to room temperature, and removing the solvent by reduced pressure distillation to obtain a crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give 73mg of the product PtON5N-tt as a yellow solid in 68% yield. 1 H NMR characterization was consistent with example 1.
Example 4: the platinum (II) complex PtON5N-tt can be synthesized by the following route:
to a reaction tube equipped with a magnetically stirred rotor were added sequentially ligand LON5N-tt (100mg, 0.14mmol,1.0 equiv), (1,5-cyclooctadiene) platinum dichloride (54mg, 0.144mmol,1.05 equiv) and sodium acetate (34mg, 0.41mmol,3.0 equiv), then nitrogen was purged three times and diethylene glycol monomethyl ether (15 mL) was added under nitrogen. The reaction was then stirred in an oil bath at 100-130 ℃ for 3 days, cooled to room temperature, and the solvent was distilled off under reduced pressure. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give the product PtON5N-tt yellow solid 71mg, 67% yield. 1 H NMR characterization was consistent with example 1.
Example 5: the platinum (II) complex PtON5N-tt can be synthesized by the following route:
to a reaction tube with a magnetically stirred rotor were added sequentially the ligand LON5N-tt (100mg, 0.14mmol,1.0 equiv), (1,5-cyclooctadiene) platinum dichloride (54mg, 0.144mmol,1.05 equiv) and sodium acetate (34mg, 0.41mmol,3.0 equiv), then nitrogen was purged three times and diethylene glycol monoethyl ether (15 mL) was added under nitrogen. The reaction was then stirred in an oil bath at 100-130 ℃ for 3 days, cooled to room temperature, and the solvent was removed by distillation under reduced pressure to give the crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give the product PtON5N-tt yellow solid 75mg in 70% yield. 1 H NMR characterization was consistent with example 1.
Example 6: the platinum (II) complex PtON5N-tt can be synthesized as follows:
to a reaction tube with a magnetically stirred rotor were added sequentially the ligand LON5N-tt (100mg, 0.14mmol,1.0 equiv), (1,5-cyclooctadiene) platinum dichloride (54mg, 0.144mmol,1.05 equiv) and sodium acetate (34mg, 0.41mmol,3.0 equiv), then nitrogen was purged three times and ethylene glycol (15 mL) was added under nitrogen. The mixture was stirred in an oil bath at 100-130 ℃ for 3 days, cooled to room temperature, and the solvent was removed by distillation under reduced pressure to give the crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give the product PtON5N-tt as a yellow solid 24mg, 23% yield. 1 H NMR characterization was consistent with example 1. The yield of the product in the embodiment is low, mainly because ethylene glycol is not stable enough, and side reactions possibly occur in solvents such as partial polymerization and the like in the presence of Lewis acid platinum metal salt; in addition, the ethylene glycol has too large polarity, the capability of stabilizing a reaction intermediate is poor, part of (1,5-cyclooctadiene) platinum dichloride is decomposed and reduced into zero-valent simple substance platinum and the like, and the mixed solution is dark gray black after the reaction is finished. However, since the synthesis method of this example has a higher boiling point, there is no risk of explosion due to high pressure, and the target product can be obtained.
Example 7: the platinum (II) complex PtON5N-tt can be synthesized by the following route:
to a reaction tube with a magnetically stirred rotor were added sequentially the ligand LON5N-tt (100mg, 0.14mmol,1.0 eq), (1,5-cyclooctadiene) platinum dichloride (54mg, 0.144mmol,1.05 eq) and sodium acetate (34mg, 0.41mmol,3.0 eq), then argon was removed three times and ethylene glycol diethyl ether (15 mL) was added under argon. Then stirring and reacting for 3 days in an oil bath kettle at the temperature of 100-120 ℃, cooling to room temperature, and removing the solvent by reduced pressure distillation to obtain a crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give the product PtON5N-tt yellow solid 72mg in 68% yield. 1 H NMR characterization was consistent with example 1.
Example 8: the platinum (II) complex PtON5N-tt can be synthesized by the following route:
to a reaction tube with a magnetically stirred rotor were added sequentially the ligand LON5N-tt (100mg, 0.14mmol,1.0 equiv), (1,5-cyclooctadiene) platinum dichloride (54mg, 0.144mmol,1.05 equiv) and sodium acetate (34mg, 0.41mmol,3.0 equiv), then nitrogen was purged three times and ethylene glycol dibutyl ether (15 mL) was added under nitrogen. Then stirring and reacting for 3 days in an oil bath kettle at the temperature of 100-130 ℃, cooling to room temperature, and removing the solvent by reduced pressure distillation to obtain a crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give the product PtON5N-tt yellow solid 26mg in 24% yield. 1 H NMR characterization was consistent with example 1. The product yield of the embodiment is low, mainly because the ethylene glycol dibutyl ether is unstable and decomposed; in addition, the ethylene glycol dibutyl ether has larger steric hindrance of terminal butyl and poorer coordination ability with a reaction intermediate, so that part (1,5-cyclooctane) can be generatedDiene) platinum dichloride is decomposed and reduced into zero-valent simple substance platinum and the like, and the mixed solution is dark gray black after the reaction is finished. However, since the synthesis method of this example has a higher boiling point, there is no risk of explosion due to high pressure, and the target product can be obtained.
Example 9: the platinum (II) complex PtON5N-tt can be synthesized by the following route:
to a reaction tube with a magnetically stirred rotor were added sequentially the ligand LON5N-tt (100mg, 0.14mmol,1.0 equiv), (1,5-cyclooctadiene) platinum dichloride (54mg, 0.144mmol,1.05 equiv) and sodium acetate (34mg, 0.41mmol,3.0 equiv), then nitrogen was purged three times and ethylene glycol monoethyl ether (15 mL) was added under nitrogen. The mixture was stirred in an oil bath at 100-130 ℃ for 3 days, cooled to room temperature, and the solvent was removed by distillation under reduced pressure to give the crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give the product PtON5N-tt yellow solid 78mg, 73% yield. 1 H NMR characterization was consistent with example 1.
Example 10: the platinum (II) complex PtON5N-tt can be synthesized by the following route:
to a reaction tube equipped with a magnetically stirred rotor were added ligands LON5N-tt (100mg, 0.14mmol,1.0 eq), (1,5-cyclooctadiene) platinum dichloride (54mg, 0.144mmol,1.05 eq) and sodium acetate (34mg, 0.41mmol,3.0 eq) in that order, then nitrogen was purged three times and ethylene glycol monopropyl ether (15 mL) was added under nitrogen. Then stirring and reacting for 3 days in an oil bath kettle at the temperature of 100-130 ℃, cooling to room temperature, and removing the solvent by reduced pressure distillation to obtain a crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give the product PtON5N-tt as a yellow solid 81mg, 76% yield. 1 H NMR characterization was consistent with example 1.
Example 11: the platinum (II) complex PtON5N-tt can be synthesized by the following route:
to a reaction tube equipped with a magnetically stirred rotor were added sequentially ligand LON5N-tt (100mg, 0.14mmol,1.0 equiv), (1,5-cyclooctadiene) platinum dichloride (54mg, 0.144mmol,1.05 equiv) and sodium acetate (34mg, 0.41mmol,3.0 equiv), then nitrogen was purged three times and ethylene glycol mono-t-butyl ether (15 mL) was added under nitrogen protection. Then stirring and reacting for 3 days in an oil bath kettle at the temperature of 100-130 ℃, cooling to room temperature, and removing the solvent by reduced pressure distillation to obtain a crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give the product PtON5N-tt as a yellow solid 29mg, 27% yield. 1 H NMR characterization was consistent with example 1. The yield of the product in the embodiment is low, mainly because the ethylene glycol mono-tert-butyl ether is stable and decomposed; in addition, because the steric hindrance of the terminal tert-butyl group of the ethylene glycol mono-tert-butyl ether is large, the coordination ability with a reaction intermediate is poor, so that part of (1,5-cyclooctadiene) platinum dichloride is decomposed and reduced into zero-valent simple substance platinum, and the like, and the mixed solution is dark gray black after the reaction is finished. However, since the synthesis method of this example has a higher boiling point, there is no risk of explosion due to high pressure, and the target product can be obtained.
Example 12: the platinum (II) complex PtON5-mm can be synthesized according to the following route:
to a reaction tube equipped with a magnetically stirred head, ligand LON5-mm (1.60g, 2.50mmol,1.0 equiv), (1,5-cyclooctadiene) platinum dichloride (980mg, 2.62mmol,1.05 equiv) and sodium acetate (615mg, 7.50mmol,3.0 equiv) were added in this order, then nitrogen was purged three times, and diethylene glycol dimethyl ether (64 mL) was added under nitrogen protection. Then at 100-130Stirring in an oil bath at the temperature of 3 days for reaction, cooling to room temperature, and distilling under reduced pressure to remove the solvent to obtain a crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give the product PtON5-mm, 780mg of yellow solid, 45% yield. 1 H NMR(500MHz,DMSO-d 6 ):δ2.43(s,3H),2.44(s,3H),4.05(s,3H),6.82(s,1H),7.11(d,J＝6.0Hz,1H),7.23(d,J＝8.5Hz,1H),7.39(t,J＝7.0Hz,1H),7.46-7.52(m,3H),7.55(s,1H),7.77(d,J＝7.0Hz,1H),7.88(d,J＝8.0Hz,1H),8.03(s,1H),8.10-8.15(m,2H),8.39(d,J＝7.5Hz,1H),9.45(d,J＝6.0Hz,1H)。 13 C NMR(125MHz,CDCl 3 ):δ21.42,21.74,34.27,106.82,108.72,110.75,111.74,112.65,114.19,114.40,115.61,116.28,116.48,116.55,119.89,119.92,122.49,122.84,123.57,124.23,129.23,132.24,134.48,136.07,138.70,143.47,149.48,150.33,150.73,152.11,154.32,155.23,193.69。HRMS(ESI):C 33 H 25 N 4 O 195 Pt[M+H] + Calcd 688.1671, found 688.1678.
Example 13: the platinum (II) complex PtON5-mi can be synthesized by the following route:
ligand LON5-mi (1.34g, 2.00mmol,1.0 equivalent), (1,5-cyclooctadiene) platinum dichloride (786 mg,2.10mmol,1.05 equivalent) and sodium acetate (492mg, 6.00mmol,3.0 equivalent) were added sequentially to a reaction tube with a magnetically stirred rotor, then nitrogen was purged three times, and diethylene glycol dimethyl ether (54 mL) was added under nitrogen protection. The mixture was reacted in an oil bath at 100-130 ℃ for 3 days with stirring, cooled to room temperature, and the solvent was removed by distillation under reduced pressure to give a crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give 860mg of the product PtON5-mi as a yellow solid in 60% yield. 1 H NMR(500MHz,DMSO-d 6 ):δ1.36(d,J＝7.0Hz,6H),2.41(s,3H),3.05-3.14(m,1H),4.03(s,3H),6.88(d,J＝1.0Hz,1H),7.09(dd,J＝6.0,1.0Hz,1H),7.24(d,J＝8.5Hz,1H),7.38(t,J＝7.5Hz,1H),7.44-7.54(m,4H),7.74(d,J＝7.5Hz,1H),7.88(d,J＝8.0Hz,1H),8.01(s,1H),8.11(dd,J＝5.5,3.0Hz,2H),8.36(d,J＝8.5Hz,1H),9.41(d,J＝6.0Hz,1H)。 13 C NMR(125MHz,CDCl 3 ):δ21.43,24.23,34.26,34.32,106.44,107.39,110.78,111.41,111.64,112.61,114.40,115.60,116.33,116.48,116.61,119.87,119.91,122.49,122.84,123.57,124.26,129.23,132.26,136.04,138.70,143.48,146.13,149.50,150.27,150.76,152.11,154.39,155.10,193.66。HRMS(ESI):C 35 H 29 N 4 O 195 Pt[M+H] + Calcd 716.1984, found 716.1990.
Example 14: the platinum (II) complex PtON5-mt can be synthesized according to the following route:
to a reaction tube equipped with a magnetically stirred head, ligand LON5-mt (1.71g, 2.50mmol,1.0 equiv), (1,5-cyclooctadiene) platinum dichloride (980mg, 2.62mmol,1.05 equiv) and sodium acetate (615mg, 7.50mmol,3.0 equiv) were added in this order, then nitrogen was purged three times, and diethylene glycol dimethyl ether (64 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 100-130 ℃ for 3 days, cooled to room temperature, and the solvent was removed by distillation under reduced pressure to give the crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give 1075mg of the product PtON5-mt as a yellow solid in 60% yield. 1 H NMR(500MHz,DMSO-d 6 ):δ1.45(s,9H),2.42(s,3H),4.05(s,3H),6.99(d,J＝1.0Hz,1H),7.10(d,J＝6.0Hz,1H),7.26(d,J＝8.0Hz,1H),7.39(t,J＝7.5Hz,1H),7.47(t,J＝7.5Hz,2H),7.54(t,J＝7.5Hz,1H),7.60(s,1H),7.77(d,J＝8.0Hz,1H),7.89(d,J＝8.0Hz,1H),8.02(s,1H),8.10-8.14(m,2H),8.27(d,J＝8.5Hz,1H),9.43(d,J＝6.5Hz,1H)。 13 C NMR(125MHz,DMSO-d 6 ):δ21.01,31.37,34.35,34.56,104.80,107.66,109.64,111.57,111.91,112.05,114.92,116.17,116.45,119.86,120.88,122.59,123.28,124.35,124.83,127.90,131.30,135.87,138.11,140.95,143.01,148.07,148.28,150.10,150.94,151.96,153.49,155.71,192.44。HRMS(ESI):C 36 H 31 N 4 O 195 Pt[M+H] + Calcd 730.2140, found 730.2131.
Example 15: the platinum (II) complex PtON5-mt can be synthesized according to the following route:
to a reaction tube with a magnetically stirred rotor were added ligand LON5-mt (341mg, 0.50mmol,1.0 equiv.), (1,5-cyclooctadiene) platinum dichloride (196mg, 0.53mmol,1.05 equiv.) and potassium acetate (147mg, 1.50mmol,3.0 equiv.) in that order, then nitrogen was purged three times and diethylene glycol dimethyl ether (20 mL) was added under nitrogen. Then stirring and reacting for 3 days in an oil bath kettle at the temperature of 100-130 ℃, cooling to room temperature, and removing the solvent by reduced pressure distillation to obtain a crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give the product PtON5-mt as a yellow solid, 195mg, 53% yield. 1 H NMR characterization was consistent with example 14.
Example 16: the platinum (II) complex PtON5-mt can be synthesized according to the following route:
to a reaction tube with a magnetically stirred rotor were added sequentially ligand LON5-mt (341mg, 0.50mmol,1.0 equiv.), (1,5-cyclooctadiene) platinum dichloride (196mg, 0.53mmol,1.05 equiv.) and potassium tert-butoxide (168mg, 1.50mmol,3.0 equiv.), then nitrogen was purged three times and diethylene glycol dimethyl ether (20 mL) was added under nitrogen. The mixture was reacted in an oil bath at 100-130 ℃ for 3 days with stirring, cooled to room temperature, and the solvent was removed by distillation under reduced pressure to give a crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give the product PtON5-mt as a yellow solid 70mg, 20% yield. 1 H NMR characterization was consistent with example 14. The yield of the product of this example is low, mainly because potassium tert-butoxide has reducibility, which can make part of (1,5-cyclooctadiene)) The platinum dichloride is decomposed and reduced into zero-valent simple substance platinum and the like. Since the synthesis method of this example has a higher boiling point, there is no risk of explosion due to high pressure, and the target product can be obtained.
Example 17: the platinum (II) complex PtON5-ti can be synthesized by the following route:
ligand LON5-ti (1.42g, 2.00mmol,1.0 equivalent), (1,5-cyclooctadiene) platinum dichloride (786 mg,2.10mmol,1.05 equivalent) and sodium acetate (492mg, 6.00mmol,3.0 equivalent) were added sequentially to a reaction tube with a magnetically stirred rotor, then nitrogen was purged three times, and diethylene glycol dimethyl ether (60 mL) was added under nitrogen protection. Then stirring and reacting for 3 days in an oil bath kettle at the temperature of 100-130 ℃, cooling to room temperature, and removing the solvent by reduced pressure distillation to obtain a crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give 709mg of PtON5-ti as a yellow solid with a yield of 60%. 1 H NMR(500MHz,DMSO-d 6 ):δ1.33(s,9H),1.36(d,J＝7.0Hz,6H),3.07-3.12(m,1H),4.05(s,3H),6.88(s,1H),7.24-7.28(m,2H),7.39(t,J＝7.5Hz,1H),7.46-7.53(m,4H),7.76(d,J＝7.5Hz,1H),7.89(d,J＝8.5Hz,1H),8.09(d,J＝8.5Hz,2H),8.15(d,J＝7.0Hz,1H),8.36(d,J＝8.0Hz,1H),9.46(d,J＝6.0Hz,1H)。 13 C NMR(125MHz,CDCl 3 ):δ24.21,29.84,34.12,34.24,35.30,106.39,107.72,110.76,111.16,111.46,112.53,112.71,114.04,115.59,116.40,116.60,119.94,122.30,122.66,123.59,124.06,129.07,132.03,135.91,138.80,143.61,145.80,149.19,150.11,152.26,154.47,155.88,163.31,193.11。HRMS(ESI):C 38 H 34 N 4 O 195 Pt[M+H] + Calcd 758.2453, found 758.2415.
Example 18: the platinum (II) complex PtON5-tt can be synthesized by the following route:
ligand LON5-tt (4.35g, 6.00mmol,1.0 equiv), (1,5-cyclooctadiene) platinum dichloride (2.36g, 6.30mmol,1.05 equiv) and sodium acetate (1.48g, 18.00mmol,3.0 equiv) were added sequentially to a reaction tube with a magnetically stirred rotor, then nitrogen was purged three times and diethylene glycol dimethyl ether (80 mL) was added under nitrogen. The mixture was stirred in an oil bath at 100-130 ℃ for 3 days, cooled to room temperature, and the solvent was removed by distillation under reduced pressure to give the crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give PtON5-tt yellow solid 3.01g with 65% yield. 1 H NMR(500MHz,DMSO-d 6 ):δ1.33(s,9H),1.46(s,9H),4.05(s,3H),6.99(s,1H),7.26-7.28(m,2H),7.39(t,J＝7.5Hz,1H),7.47-7.55(m,3H),7.59(s,1H),7.76(d,J＝7.5Hz,1H),7.89(d,J＝8.5Hz,1H),7.08-7.10(m,2H),8.15(d,J＝7.5Hz,1H),8.25(d,J＝8.0Hz,1H),9.46(d,J＝6.0Hz,1H)。 13 C NMR(125MHz,CDCl 3 ):δ29.99,31.66,34.29,34.85,35.47,105.22,107.25,110.70,110.79,111.50,112.60,113.15,114.04,115.59,116.37,116.47,116.51,120.01,122.38,122.77,123.62,124.27,129.16,132.21,136.01,138.83,143.59,148.37,149.46,150.16,152.03,154.57,155.52,163.46,193.48。HRMS(ESI):C 39 H 37 N 4 O 195 Pt[M+H] + Calcd 772.2610, found 772.2614.
Example 19: the platinum (II) complex PtON7p-mt can be synthesized according to the following route:
ligand LON7p-mt (1.14g, 1.61mmol,1.0 equivalent), (1,5-cyclooctadiene) platinum dichloride (632mg, 1.69mmol,1.05 equivalent) and sodium acetate (396mg, 4.83mmol,3.0 equivalent) were added sequentially to a reaction tube with a magnetic stirrer, then nitrogen was purged three times, and diethylene glycol dimethyl ether (45 mL) was added under nitrogen protection. The reaction was then stirred in an oil bath at 100-130 ℃ for 3 days, cooled to room temperature, and the solvent was removed by distillation under reduced pressure to give the crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum productsThe volume ratio of ether/dichloromethane was 10-2:1 to give 830mg of PtON7p-mt as a yellow solid in 68% yield. 1 H NMR(500MHz,DMSO-d 6 ):δ1.38(s,9H),2.42(s,3H),3.86(s,3H),6.88(d,J＝1.5Hz,1H),7.12(dd,J＝6.0,1.0Hz,1H),7.21(d,J＝8.0Hz,1H),7.36-7.39(m,2H),7.43-7.47(m,1H),7.49-7.53(m,1H),7.58(t,J＝7.5Hz,2H),7.74-7.76(m,2H),7.85(d,J＝8.0Hz,1H),8.00(s,1H),8.08(d,J＝8.0Hz,1H),8.12(d,J＝7.5Hz,1H),8.42(s,1H),9.50(d,J＝6.0Hz,1H)。
Example 20: the platinum (II) complex PtON7p-tt can be synthesized by the following route:
ligand LON7p-tt (908mg, 1.21mmol,1.0 eq), (1,5-cyclooctadiene) platinum dichloride (475mg, 1.27mmol,1.05 eq) and sodium acetate (298mg, 3.63mmol,3.0 eq) were added sequentially to a reaction tube with a magnetically stirred rotor, then nitrogen was purged three times and diethylene glycol dimethyl ether (36 mL) was added under nitrogen. Then stirring and reacting for 3 days in an oil bath kettle at the temperature of 100-130 ℃, cooling to room temperature, and removing the solvent by reduced pressure distillation to obtain a crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a lotion: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give the product PtON7p-tt yellow solid 570mg in 59% yield. 1 H NMR(500MHz,DMSO-d 6 ):δ1.35(s,9H),1.38(s,9H),3.88(s,3H),6.89(d,J＝2.0Hz,1H),7.22(d,J＝8.5Hz,1H),7.32(dd,J＝6.5,2.0Hz,1H),7.38(t,J＝7.5Hz,2H),7.45-7.53(m,2H),7.58(t,J＝8.0Hz,2H),7.75-7.77(m,2H),7.87(d,J＝8.5Hz,1H),8.07-8.09(m,2H),8.14(d,J＝7.5Hz,1H),8.43(s,1H),9.55(d,J＝6.0Hz,1H)。 13 C NMR(125MHz,CDCl 3 ):δ30.12,31.51,34.72,35.54,36.14,103.16,106.72,111.05,112.77,113.38,113.63,114.05,115.22,115.60,115.80,116.03,120.02,122.35,123.54,128.67,128.94,129.29,134.41,138.87,143.62,148.31,148.70,149.62,152.49,154.62,155.11,163.21,185.84。
Comparative example 1: the platinum (II) complex PtON5-mt can be synthesized according to the following route:
to a lock with magnetically stirred rotor was added the ligand LON5-mt (341mg, 0.50mmol,1.0 equiv.), platinum dichloride (196mg, 0.53mmol,1.05 equiv.), sodium acetate (123mg, 1.50mmol,3.0 equiv.) and 1,5-cyclooctadiene in that order, then nitrogen was purged three times and tetrahydrofuran (20 mL) was added under nitrogen blanket. The reaction was then stirred in an oil bath at 100-130 ℃ for 3 days, cooled to room temperature, and the solvent was removed by distillation under reduced pressure to give the crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give 122mg of yellow solid in 34% yield. 1 H NMR characterization was consistent with example 14.
Comparative example 2: the platinum (II) complex PtON5-mt can be synthesized according to the following route:
to a sealed tube with a magnetically stirred rotor was added sequentially ligand LON5-mt (341mg, 0.50mmol,1.0 equiv.), (1,5-cyclooctadiene) platinum dichloride (196mg, 0.53mmol,1.05 equiv.) and sodium acetate (123mg, 1.50mmol,3.0 equiv.), then nitrogen was purged three times and 2-methyltetrahydrofuran (20 mL) was added under nitrogen. Then stirring and reacting for 3 days in an oil bath kettle at the temperature of 100-130 ℃, cooling to room temperature, and removing the solvent by reduced pressure distillation to obtain a crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1 to give 93mg of yellow solid with 26% yield. 1 H NMR characterization was consistent with example 14.
Comparative example 3: the platinum (II) complex PtON5-mt can be synthesized according to the following route:
to a sealed tube with a magnetic stirrer was added the ligand LON5-mt (341mg, 0.50mmol,1.0 eq.) in that order(1,5-cyclooctadiene) platinum dichloride (196mg, 0.53mmol,1.05 equiv.) and sodium acetate (123mg, 1.50mmol,3.0 equiv.), then nitrogen was purged three times and dioxane (20 mL) was added under nitrogen. The reaction was then stirred in an oil bath at 100-130 ℃ for 3 days, cooled to room temperature, and the solvent was removed by distillation under reduced pressure to give the crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a lotion: the volume ratio of petroleum ether/dichloromethane was 10-2:1, yielding 100mg of yellow solid in 28% yield. 1 H NMR characterization was consistent with example 14.
Comparative example 4: the platinum (II) complex PtON5-mt can be synthesized according to the following route:
to a sealed tube with a magnetically stirred rotor was added sequentially ligand LON5-mt (341mg, 0.50mmol,1.0 equiv.), (1,5-cyclooctadiene) platinum dichloride (196mg, 0.53mmol,1.05 equiv.) and sodium acetate (123mg, 1.50mmol,3.0 equiv.), then nitrogen was purged three times and acetonitrile (20 mL) was added under nitrogen. Then stirring and reacting for 3 days in an oil bath kettle at the temperature of 100-130 ℃, cooling to room temperature, and removing the solvent by reduced pressure distillation to obtain a crude product. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: the volume ratio of petroleum ether/dichloromethane was 10-2:1, and 142mg of yellow solid was obtained with a yield of 40%. 1 H NMR characterization was consistent with example 14.
The synthesis method of the embodiments 1-20 of the invention adopts the solvent molecules with bidentate or multidentate coordination capability to stabilize the reaction intermediate of the metal organic platinum (II), thereby greatly improving the separation yield of the reaction; more importantly, because the solvent molecules with bidentate or polydentate coordination capability have very high boiling points, the reaction can be carried out in a conventional non-closed reaction device without sealing a pipe; even if a tube sealing is used, the boiling point of the reaction solvent is high and is higher than the heating temperature of the reaction, so that the pressure in the reaction system can be greatly reduced, and the risk of explosion is avoided. In addition, the solvents developed in the method have very high flash points, and are far higher than tetrahydrofuran (flash point: -14 ℃) and the like used in the prior art. Whereas tetrahydrofuran (boiling point: 66 ℃ C.; flash point: minus 14 ℃ C.) used in comparative examples 1-4, 2-methyltetrahydrofuran (boiling point: 78 ℃ C.), dioxane (boiling point: 101 ℃ C.; flash point: 12 ℃ C.) and acetonitrile (boiling point: 81.6 ℃ C.; flash point: 12.8 ℃ C.) used had low boiling points, and tube closures were required, with high internal pressure and high explosion risk; and its flash point is also low.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples of practicing the invention, and that various changes in form and detail may be made therein without departing from the spirit and scope of the invention in practice. For example, many of the substituent structures described herein may be substituted with other structures without departing from the spirit of the invention. The base sodium acetate used in the reaction may be replaced with other alkali metal acetates, deuterated alkali metal salts, alkali metal carbonates, alkali metal bicarbonates, alkali metal phosphates, alkali metal acid phosphates, alkali metal alkoxides, deuterated alkali metal alkoxides, and the like. The (1,5-cyclooctadiene) platinum dichloride used in the reaction can be replaced with other divalent platinum metal salts, such as (1,3,5,7-cyclooctatetraene) platinum dichloride, potassium tetrachloroplatinate, sodium tetrachloroplatinate, platinum dichloride, and the like.
Description of the reaction time: the influence of the reaction time on the reaction yield is mainly reflected in the degree of progress of the reaction, and generally, most of the ligand can be reacted within 0.5 to 5 days.
The four-tooth ring metal platinum complexes based on the carbene ligands synthesized in the embodiments 1-20 of the invention are all deep blue light phosphorescent materials, have the characteristics of high thermal decomposition temperature, high quantum effect, narrow emission spectrum and the like, and have great application prospects in the field of blue light phosphorescent materials.
Thermogravimetric analysis: the thermogravimetric analysis curves were all completed on TGA2 (SF) thermogravimetric analysis. The thermogravimetric analysis test conditions were: the testing temperature is 50-700 ℃; the heating rate is 20K/min; the crucible is made of aluminum oxide; and testing is completed under nitrogen atmosphere; the sample mass is generally 2-5mg. FIG. 2 is a thermogravimetric plot of 5-mm of example 12PtON with a thermal decomposition temperature greater than 400 ℃.
And (3) photophysical analysis: phosphorescence emission spectrum andthe linear lifetime was tested on a HORIBA FL3-11 spectrometer. And (3) testing conditions: in the room temperature emission spectrum, all samples were dichloromethane (chromatographic grade) dilute solutions (10) -5 -10 -6 M), and the samples are prepared in a glove box, and nitrogen is introduced for 5 minutes; the triplet state lifetime measurements were all measured at the most intense peak of the sample emission spectrum. The tetradentate ring metal platinum complexes are all deep blue phosphorescence luminescent materials, the maximum emission wavelengths of the tetradentate ring metal platinum complexes are all shown in the figure 3, and the emission spectra of PtON5-mm in 2-methyltetrahydrofuran at 77K and in dichloromethane solution at room temperature are shown in the figure. FIG. 4 is an emission spectrum of PtON7p-tt in 2-methyltetrahydrofuran at 77K and in dichloromethane at room temperature. FIG. 5 is an emission spectrum of PtON5N-tt in 2-methyltetrahydrofuran at 77K and in dichloromethane at room temperature. As can be seen from fig. 3-5 and table 1: the tetradentate ring metal platinum complexes containing carbene ligands prepared in embodiments 1-20 of the invention are all phosphorescent luminescent materials with narrow emission spectra, and the maximum emission wavelengths of the complexes are all in a deep blue light region of 448-466nm at room temperature, so that the complexes are deep blue luminescent materials urgently needed in the field of OLED at present.
TABLE 1 partial physical property characterization of the four-ring metal platinum complex deep blue light phosphorescence luminescent material
FWHM is the full width at half maximum.
The technical scheme of the invention can be applied to the synthesis of the carbene-based tetradentate ring metal platinum complex in the embodiment, and can also be applied to the synthesis of other types of carbene-based tetradentate or tridentate ring metal platinum complexes:
wherein L is 1 、L 2 、L 3 And L 4 Are each independently a five-or six-membered carbocyclic ring, heterocyclic ring, heteroaromatic ring, at least one of which is a carbene ligand;
wherein V 1 、V 2 、V 3 And V 4 Is coordinated to platinum and is independently N and C;
A 1 、A 2 and A 3 Each independently O, S, CH 2 、CD 2 、CR a R b 、C＝O、SiR a R b 、GeH 2 、GeR a R b 、NH、NR c 、PH、PR c 、R c P＝O、AsR c 、R c As＝O、S＝O、SO 2 、Se、Se＝O、SeO 2 、BH、BR c 、R c Bi = O, biH, or BiR c ；A 1 、A 2 And A 3 Each independently empty (i.e., two adjacent ls are directly connected).
Wherein R is 1 、R 2 、R 3 And R 4 Each independently represents mono-, di-, tri-, or tetra-substituted or unsubstituted, with R 1 、R 2 、R 3 And R 4 Each independently is hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imine, sulfo, carboxyl, hydrazine, substituted silyl, a polymeric group, or a combination thereof. Simultaneous, two or more adjacent R 1 、R 2 、R 3 And R 4 May be optionally joined to form fused rings.
Claims (5)
1. A synthesis method for metallization of a platinum carbene phosphorescent material is characterized in that a molecule with a boiling point of 120-250 ℃ and bidentate or multidentate coordination capacity is used as a solvent, and under the protection of alkali and inert gas, a tridentate or tetradentate ligand containing carbene and a platinum metal salt are mixed according to a molar ratio of (0.94-0.97): 1, adding the raw materials into a solvent, reacting for 0.5-5.0 days at the temperature of 95-130 ℃, distilling under reduced pressure to remove the solvent, and separating and purifying by using a silica gel chromatographic column to obtain a metallized platinum carbene phosphorescent material; the volume mol ratio of the solvent to the tridentate or tetradentate ligand containing the carbene is 13-108:1, the ligand to base equivalent ratio is 1:3; the metallized platinum carbene phosphorescent material has the following structure:
wherein L is 1 Is a carbene ligand;
R 1 、R 2 、R 3 、R 4 and R 5 Each independently may be mono-, di-, tri-, tetra-, or unsubstituted; r is 1 、R 2 、R 3 、R 4 And R 5 Each independently represents hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, nitrile, alkoxycarbonyl, alkylthio, substituted silyl, or a combination thereof;
at the same time, two adjacent R 1 May be optionally linked to form a fused ring;
the structure of the solvent is shown as follows:
2. the method for synthesizing platinum carbene phosphorescent material metallization according to claim 1, wherein the inert gas is argon or nitrogen.
3. The synthesis method of the platinum carbene phosphorescent material metallization, as recited in claim 1, wherein the base is one or more of alkali metal acetate, alkali metal carbonate, alkali metal bicarbonate, alkali metal phosphate, alkali metal bicarbonate and alkali metal alcoholate mixed according to any proportion.
4. The method for synthesizing platinum carbene phosphorescent material through metallization according to claim 1, wherein the platinum metal salt is potassium tetrachloroplatinate, sodium tetrachloroplatinate, platinum dichloride, (1,5-cyclooctadiene) platinum dichloride or (1,3,5,7-cyclooctatetraene) platinum dichloride.
5. The method for synthesizing the platinum carbene phosphorescent material metallization according to claim 1, wherein the metallized platinum carbene phosphorescent material has the following structure:
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