CN113292604B - N-heterocarbene-based 5/6/6 parallel ring four-tooth ring metal platinum (II) complex phosphorescent material and application thereof - Google Patents
N-heterocarbene-based 5/6/6 parallel ring four-tooth ring metal platinum (II) complex phosphorescent material and application thereof Download PDFInfo
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- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 title claims abstract description 26
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- 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 description 3
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- BPMFPOGUJAAYHL-UHFFFAOYSA-N 9H-Pyrido[2,3-b]indole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=N1 BPMFPOGUJAAYHL-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 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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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
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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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- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
Abstract
The invention provides a 5/6/6 parallel ring four-tooth ring metal platinum (II) complex phosphorescence material based on N-heterocarbene and application thereof. N-heterocyclic carbene ligand in the 5/6/6 parallel ring four-tooth ring metal platinum (II) complex phosphorescent material based on N-heterocyclic carbene has strong sigma electron donating ability and weak pi electron withdrawing ability, and can form strong coordination bond in the coordination process with metal atoms. Meanwhile, the tetradentate ring metal platinum (II) complex molecule has stronger rigidity, can limit the vibration and rotation of the molecule, and reduces non-radiative transition.
Description
Technical Field
The invention relates to a phosphorescent material and application thereof, in particular to a 5/6/6 parallel ring four-tooth ring platinum (II) complex phosphorescent material based on N-heterocarbene and application thereof.
Background
Compared with a Liquid Crystal Display (LCD), an Organic Light Emitting Diode (OLED) has the advantages of being foldable or bendable, self-luminous, high in contrast ratio, wide in working temperature range, low in material cost, high in luminous efficiency, low in power consumption and the like. It is expected that with barrier breakthrough and cost reduction of future OLED technologies, OLED displays will become the mainstream of future displays.
The design and development of luminescent materials is the core of the OLED field. The traditional fluorescent luminescent material can use 25% of singlet excitons at most, the rest 75% of triplet excitons are deactivated due to forbidden transition, and phosphorescent materials with heavy atomic effect can fully utilize the singlet excitons and the triplet excitons to obtain the utilization rate of 100% of excitons. Phosphorescent guest materials play a decisive role in the efficiency of phosphorescent electroluminescent devices, the performance of which can be tuned by designing different types of organic ligands. The design and development of new phosphorescent emitters remains a key issue in promoting the development of OLED technology, and low driving voltage and high luminance and long life OLED devices remain the goal of this technology development. The ligand with N-heterocyclic carbene has strong sigma electron donating ability and weak pi electron withdrawing ability, can form strong coordination bond in the coordination process with metal atoms, and meanwhile, the LUMO energy level of the N-heterocyclic carbene ligand molecule is high, so that the band gap of the molecule is enlarged, and the molecule can emit blue shift.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a 5/6/6 parallel ring four-tooth ring metal platinum (II) complex phosphorescence material based on N-heterocarbene and application thereof.
To achieve the above object: the invention provides:
a5/6/6 parallel ring four-tooth ring metal platinum (II) complex phosphorescence material based on N-hetero-carbene has a chemical formula shown in a general formula (1):
R a 、R b 、R c and R is d Each independently is hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or di-alkylamino, mono-or di-arylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoryl, imino, sulfo, carboxyl, hydrazino, substituted silyl, polymeric groups, or combinations thereof;
R 1 、R 2 、R 3 、R 4 、R 5 、R 6 and R is 7 Each independently is hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, heterocyclyl, alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heteroaryl, haloalkyl, halogen, hydroxy, mercapto, nitro, cyano, amino, carboxyl, sulfo, hydrazino, ureido, alkynyloxy, ester, amido, sulfonyl, sulfinyl, sulfonamido, phosphoramido, alkoxycarbonylamino, aryloxycarbonylamino, silyl, alkylamino, dialkylamino, monoarylamino,biarylamino, ureylene, imino, or combinations thereof. R is R 1 、R 2 、R 3 、R 4 、R 5 、R 6 And R is 7 May be connected to form a condensed ring, and the condensed ring may be condensed with other rings.
Further, the structural formula of the general formula (1) includes, but is not limited to, the following structure:
further, the use of N-heterocarbene-based 5/6/6-ring tetracyclic platinum (II) complex phosphorescent materials in organic light emitting devices. The organic light emitting element is an organic light emitting diode, a light emitting diode or a light emitting electrochemical cell.
Further, the organic light emitting element includes a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode; the organic layer comprises a 5/6/6 fused ring four-tooth ring metal platinum (II) complex phosphorescent material based on N-heterocarbene.
The beneficial effects of the invention are as follows: the N-heterocyclic carbene ligand in the N-heterocyclic carbene-based 5/6/6 parallel ring four-tooth ring metal platinum (II) complex phosphorescent material has strong sigma electron donating ability and weaker pi electron withdrawing ability, and can form strong coordination bonds and feedback pi bonds from metal to empty p orbitals of carbon atoms in the coordination process of the N-heterocyclic carbene-based 5/6/6 parallel ring four-tooth ring metal platinum (II) complex phosphorescent material. At the same time, the LUMO energy level of the N-heterocyclic carbene ligand molecule is higher, so that the band gap of the molecule is enlarged, and the blue shift of the molecule emission can be realized. Meanwhile, the tetradentate ring metal platinum (II) complex molecule has stronger rigidity, can limit the vibration and rotation of the molecule, and reduces non-radiative transition.
Drawings
FIG. 1 is a graph showing emission spectra of PtLS1, ptLS2, and PtLS3 at 77K in 2-methyltetrahydrofuran;
FIG. 2 is a graph showing emission spectra of PtLS1, ptLS2, and PtLS3 in methylene chloride solution at room temperature;
FIG. 3 is a graph of emission spectra of PtLS1, ptLS2, and PtLS3 in polymethyl methacrylate (PMMA) at room temperature;
FIG. 4 is a graph showing absorption spectra of PtLS1, ptLS2 and PtLS3 in methylene chloride solution at room temperature;
FIG. 5 is a schematic diagram of N-heterocarbene forming coordination bond and feedback pi bond with metal;
FIG. 6 is a schematic structural view of an organic light emitting device;
FIG. 7 is an electroluminescence spectrum of PtLS1 as a doped luminescent material OLED device;
fig. 8 is a graph of the current-external quantum efficiency of PtLS1 as a doped luminescent material OLED device.
Detailed Description
The following describes the present invention in detail. The following description of the constituent elements may be based on the representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples.
The compound contained in the N-heterocarbene-based 5/6/6-ring four-tooth ring metal platinum (II) complex phosphorescent material has the structure shown in the following general formula (1).
The synthetic route of the complex in the general formula (1) is as follows:
example 1: the synthetic route of the four-tooth ring metal platinum (II) complex phosphorescent material PtLS1 is shown as follows:
(1) Intermediate ACzbpHO 2 Is synthesized by the following steps: to a dry tube sealer with a magnetic rotor were added in order 4 '-iodo-2-nitro-1, 1' -biphenyl (500 mg,4.46mmol,1.5 eq), azacarbazole (1.45 g,2.97mmol,1.0 eq), cuprous iodide (56 mg,2.97mmol,10 mol%), trans-1, 2-cyclohexanediamine (399 mg,2.97mmol,10 mol%) and sodium t-butoxide (600 mg,6.24mmol,2.1 eq.) followed by three nitrogen exchanges and dimethyl sulfoxide (13 mL) under nitrogen protection. The above operation was repeated three times. The four sealed tubes were stirred in an oil bath at 110 ℃ for 1 day each, cooled to room temperature, the four reaction solutions were mixed, extracted with ethyl acetate, the organic layer was washed twice with water, and the aqueous layer was extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure. The crude product is separated and purified by a silica gel chromatographic column, and the leaching agent: petroleum ether/dichloromethane/ethyl acetate=8:2:1, giving the product aczbphono 2 Yellow solid 2.07g, yield 48%. 1 H NMR(500MHz,CDCl 3 ):δ7.29(dd,J＝8.0Hz,1H),7.38(t,J＝7.5Hz,1H),7.51-7.61(m,6H),7.67-7.70(m,1H),7.75(d,J＝8.5Hz,2H),7.92-7.94(m,1H),8.15(d,J＝7.5Hz,1H),8.45(d,J＝7.5Hz,1H),8.52-8.53(m,1H)。
(2) Synthesis of intermediate ACzCzH: to a dry three-neck flask with a thermometer with a magnetic rotor was added aczbphono in sequence 2 (603 mg,1.64mmol,1.0 eq.) triphenylphosphine (1.29 g,4.92mmol,3.0 eq.) was then replaced with nitrogen three times and o-dichlorobenzene (15 mL) was added under nitrogen. The mixture was stirred in an electric heating mantle at 180 ℃ for 1 day, cooled to room temperature, and the solvent was distilled off under reduced pressure. The crude product is separated and purified by a silica gel chromatographic column, and the leaching agent: petroleum ether/dichloromethane/ethyl acetate=8:2:1, giving the product ACzCzH as a tan solid 475mg in 85% yield. 1 H NMR(500MHz,DMSO-d 6 ):δ7.22-7.25(m,1H),7.35-7.41(m,3H),7.40-7.46(m,1H),7.52-7.53(m,2H),7.56(d,J＝8.5Hz,1H),7.74(d,J＝1.5Hz,1H),8.22(d,J＝7.5Hz,1H),8.34(t,J＝8.0Hz,2H),8.45(dd,J＝5.0,1.5Hz,1H),8.67(dd,J＝8.0,1.5Hz,1H),11.46(s,1H)。 13 C NMR(126MHz,CDCl 3 ):δ110.31,110.68,110.97,115.76,116.71,118.15,118.91,120.11,120.34,120.64,120.76,120.83,122.47,122.90,125.56,127.13,128.84,132.92,140.43,140.79,141.04,145.54,152.27。
(3) 1-t synthesis: to a tube sealer with a magnetic stirrer rotor was added 1-Br (112 mg,0.40mmol,1.0 eq), ACzCzH (133 mg,0.40mmol,1.0 eq), tris (dibenzylideneacetone) dipalladium (15 mg,0.016mmol,4 mol%), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (13 mg,0.032mmol,8 mol%), sodium t-butoxide (77 mg,0.80mmol,2.0 eq) followed by three nitrogen substitutions and toluene (5 mL) under nitrogen. Then stirring and reacting for 3 days in an oil bath at 120 ℃, cooling to room temperature, and distilling off the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by a silica gel chromatographic column, and the leaching agent: the volume ratio of petroleum ether/ethyl acetate was 6:1-2:1, yielding 121mg of product 1-t as a white foamy solid in 58% yield. 1 H NMR(500MHz,CDCl 3 ):δ1.41(s,9H),7.24-7.26(m,2H),7.32-7.40(m,3H),7.43-7.50(m,4H),7.54-7.57(m,2H),7.59(dd,J＝8.5,2.0Hz,1H),7.74(t,J＝2.0Hz,1H),7.76(d,J＝1.5Hz,1H),8.06(s,1H),8.13(d,J＝7.5Hz,1H),8.23(d,J＝8.0Hz,1H),8.36(d,J＝8.5Hz,1H),8.39(dd,J＝7.5,1.5Hz,1H),8.48(dd,J＝8.5,2.0Hz,1H). 13 C NMR(126MHz,CDCl 3 ):δ31.16,35.30,109.07,109.62,110.37,116.12,116.35,117.03,117.56,118.38,119.59,120.64,120.72,120.74,120.78,120.93,121.29,122.94,123.26,123.29,126.44,126.90,128.28,130.38,134.24,135.60,138.45,138.62,140.32,141.03,141.17,146.44,152.12,155.65.
(4) Synthesis of Ligand 1: to a closed tube with a magnetic stirrer rotor was added 1-t (1.30 g,2.50mmol,1.0 eq.) followed by three nitrogen exchanges and methyl iodide (426 mg,3.0mmol,1.2 eq.) and toluene (30 mL) under nitrogen. Then stirring and reacting for 2 days in an oil bath at 100 ℃, cooling to room temperature, adding petroleum ether (30 mL), filtering after ultrasonic treatment, leaching a filter cake by using petroleum ether, pumping to dry the filter cake, transferring the filter cake into a reaction tube, adding methanol (30 mL) solution, adding water (20 mL) solution of ammonium hexafluorophosphate (544 mg,3.75mmol,1.5 eq.) into the reaction tube, stirring for 3 days at room temperature, removing methanol by reduced pressure distillation, adding water for pumping filtration, leaching the filter cake by using water, and obtaining a crude product. The crude product is separated and purified by a silica gel chromatographic column, and the leaching agent: the volume ratio of dichloromethane to ethyl acetate is 10:1-1:1, and the product Ligand1 is obtained as white powdery solid 1.46g, and the yield is 84%. 1 H NMR(500MHz,DMSO-d 6 ):δ1.41(s,9H),3.90(s,3H),7.33-7.38(m,2H),7.42(t,J＝7.0Hz,1H),7.48-7.51(m,1H),7.53-7.56(m,1H),7.59-7.65(m,3H),7.73(d,J＝1.5Hz,1H),7.85(t,J＝1.5Hz,1H),7.89(t,J＝1.5Hz,1H),7.99-8.01(m,2H),8.30(d,J＝8.0Hz,1H),8.35(t,J＝2.0Hz,1H),8.39-8.40(m,2H),8.53(d,J＝8.5Hz,1H),8.64(dd,J＝7.5,1.5Hz,1H),9.77(s,1H). 13 CNMR(126MHz,DMSO-d 6 ):δ30.77,35.39,36.12,108.70,110.06,110.39,115.74,116.60,117.41,118.20,119.77,120.41,120.92,120.97,121.00,121.26,121.45,121.53,122.14,122.71,124.19,124.73,126.85,127.24,129.00,134.12,136.11,136.39,137.87,139.57,140.22,140.61.
(5) Synthesis of PtLS 1: to a tube sealer with a magnetic stirring rotor, ligand Ligand1 (97 mg,0.14mmol,1.0 eq), (1, 5-cyclooctadiene) platinum dichloride (58 mg,0.154mmol,1.1 eq) and sodium acetate (35 mg,0.42mmol,3.0 eq) were added in sequence, then nitrogen was purged three times, diethylene glycol dimethyl ether (3 mL) was added under nitrogen protection, and nitrogen bubbling was carried out 3 timesAnd 0 minutes. Then stirring and reacting for 3 days in an oil bath at 120 ℃, cooling to room temperature, and distilling off the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by a silica gel chromatographic column, and the leaching agent: the volume ratio of petroleum ether/dichloromethane is 5:1-1:1, and the product PtLS1 is obtained as a yellow solid 31mg with a yield of 30%. 1 H NMR(500MHz,DMSO-d 6 ):δ1.46(s,9H),3.56(s,3H),7.31(t,J＝7.0Hz,1H),7.40(d,J＝1.5Hz,1H),7.42(d,J＝1.0Hz,1H),7.46-7.54(m,3H),7.70-7.73(m,1H),7.80(d,J＝8.0Hz,1H),7.97(d,J＝8.0Hz,2H),8.20-8.28(m,4H),8.44(d,J＝7.5Hz,1H),8.98(d,J＝7.5Hz,1H),9.42(dd,J＝5.5,1.0Hz,1H). 13 C NMR(126MHz,DMSO-d6):δ31.47,34.95,37.42,104.57,109.40,110.63,114.06,115.15,116.02,116.36,117.13,117.29,119.43,120.25,120.29,122.17,122.31,122.35,123.24,124.82,126.11,126.32,127.97,130.31,135.86,136.96,138.93,139.22,141.93,146.90,146.96,149.15,153.35,180.47.
Example 2: the synthetic route of the four-tooth ring metal platinum (II) complex phosphorescent material PtLS2 is shown as follows:
(1) 2-t synthesis: to a tube sealer with a magnetic stirrer rotor was added 2-Br (99 mg,0.30mmol,1.0 eq), ACzCzH (100 mg,0.30mmol,1.0 eq), tris (dibenzylideneacetone) dipalladium (11 mg,0.012mmol,4 mol%), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (10 mg,0.024mmol,8 mol%), sodium t-butoxide (58 mg,0.60mmol,2.0 eq) followed by three nitrogen substitutions and toluene (3 mL) under nitrogen. Then stirring and reacting for 3 days in an oil bath at 120 ℃, cooling to room temperature, and distilling off the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by a silica gel chromatographic column, and the leaching agent: the volume ratio of petroleum ether/ethyl acetate is 6:1-4:1, and 108mg of white foam solid of the product 2-t is obtained, and the yield is 62%. 1 H NMR(500MHz,DMSO-d 6 ):δ1.41(s,9H),7.20(t,J＝7.5Hz,1H),7.28(t,J＝7.5Hz,1H),7.32-7.41(m,3H),7.47(t,J＝7.5Hz,1H),7.54(t,J＝7.0Hz,1H),7.61-7.67(m,4H),7.75-7.77(m,2H),7.82(d,J＝1.5Hz,1H),7.87-7.88(m,2H),8.30(d,J＝7.5Hz,1H),8.36-8.39(m,2H),8.52(d,J＝8.5Hz,1H),8.63-8.66(m,2H). 13 C NMR(126MHz,CDCl 3 ):δ31.21,35.39,109.13,109.67,110.38,110.42,116.12,116.36,119.19,119.74,120.02,120.68,120.75,120.79,120.94,121.35,123.05,123.08,123.35,123.80,124.02,126.49,126.95,128.29,133.39,134.30,135.78,137.44,138.84,140.41,141.11,141.23,142.03,143.66,146.48,152.18,155.84.
(2) Synthesis of Ligand 2: to a tube closure with a magnetic stirrer rotor was added 2-t (29 mg,0.50mmol,1.0 eq.) followed by three nitrogen exchanges and methyl iodide (85 mg,0.60mmol,1.2 eq.) and toluene (7 mL) under nitrogen. Then stirring and reacting for 2 days in an oil bath at 100 ℃, cooling to room temperature, adding petroleum ether (7 mL), filtering after ultrasonic treatment, leaching a filter cake by using petroleum ether, pumping to dry the filter cake, transferring the filter cake into a reaction tube, adding methanol (7 mL) solution, adding water (4 mL) solution of ammonium hexafluorophosphate (109 mg,0.75mmol,1.5 equivalent), stirring for 3 days at room temperature, removing methanol by reduced pressure distillation, adding water for pumping filtration, leaching the filter cake by using water, and obtaining a crude product. The crude product is separated and purified by a silica gel chromatographic column, and the leaching agent: the volume ratio of dichloromethane/ethyl acetate was 10:1-1:1, yielding 265mg of product Ligand2 as a white powdery solid in 71% yield. 1 H NMR(500MHz,DMSO-d 6 ):δ1.44(s,9H),4.14(s,3H),7.34-7.38(m,2H),7.42(t,J＝7.5Hz,1H),7.47(t,J＝7.0Hz,1H),7.53-7.59(m,2H),7.62-7.67(m,3H),7.74(t,J＝7.5Hz,1H),7.81(d,J＝1.5Hz,1H),7.89(d,J＝8.0Hz,1H),7.92(t,J＝1.5Hz,1H),8.01(t,J＝1.5Hz,1H),8.11(d,J＝8.5Hz,1H),8.15(t,J＝1.5Hz,1H),8.31(d,J＝7.5Hz,1H),8.38-8.41(m,2H),8.54(d,J＝8.0Hz,1H),8.66(dd,J＝7.5,1.5Hz,1H),10.15(s,1H).13C NMR(126MHz,DMSO-d6):δ30.78,33.44,35.36,108.80,110.05,110.37,113.52,113.83,115.74,116.58,119.83,120.39,120.95,121.04,121.43,121.46,121.53,122.22,122.79,125.51,126.83,126.89,127.26,127.39,129.02,131.00,131.77,134.11,134.47,137.97,139.60,140.22,140.57,143.43,146.31,151.40,155.61.
(3) Synthesis of PtLS 2: to a tube closure with a magnetic stirrer was added the Ligand Ligand2 (237 mg,0.32mmol,1.0 eq.) and (1, 5-cyclooctadiene) platinum dichloride (132 mg,0.352mmol,1.1Amount) and sodium acetate (79 mg,0.96mmol,3.0 eq.) were added, followed by pumping nitrogen three times, diethylene glycol dimethyl ether (10 mL) was added under nitrogen protection, and nitrogen bubbling was carried out for 30 minutes. Then stirring and reacting for 3 days in an oil bath at 120 ℃, cooling to room temperature, and distilling off the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by a silica gel chromatographic column, and the leaching agent: the volume ratio of petroleum ether/dichloromethane is 5:1-1:1, and the product PtLS2 is obtained as a yellow solid 56mg with a yield of 22%. 1 H NMR(500MHz,DMSO-d 6 ):δ1.56(s,9H),3.63(s,3H),7.34(t,J＝7.0Hz,1H),7.48(t,J＝7.5Hz,1H),7.52-7.57(m,4H),7.72-7.77(m,3H),7.93(d,J＝7.0Hz,1H),8.05(d,J＝8.5Hz,1H),8.12(d,J＝1.5Hz,1H),8.27(dd,J＝7.5,1.0Hz,1H),8.31-8.34(m,3H),8.48(d,J＝7.5Hz,1H),9.05(dd,J＝7.5,1.5Hz,1H),9.40(dd,J＝5.5,1.0Hz,1H). 13 C NMR(126MHz,CDCl 3 ):δ31.76,34.21,35.18,105.71,110.60,110.67,111.01,111.59,114.51,115.35,115.51,116.01,117.15,118.13,120.04,120.12,120.30,121.15,122.07,122.51,122.72,124.16,124.39,126.52,126.84,127.66,128.70,132.12,136.27,136.32,137.69,139.98,140.41,142.58,147.10,147.77,150.57,152.16,192.27.
Example 3: the synthetic route of the four-tooth ring metal platinum (II) complex phosphorescent material PtLS3 is shown as follows:
(1) Synthesis of 3-t: to a tube closure with a magnetic stirrer rotor was added 3-Br (50 mg,0.15mmol,1.0 eq), ACzCzH (50 mg,0.15mmol,1.0 eq), tris (dibenzylideneacetone) dipalladium (6 mg,0.006mmol,4 mol%), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (5 mg,0.012mmol,8 mol%), sodium t-butoxide (29 mg,0.30mmol,2.0 eq) followed by three nitrogen substitutions and toluene (2 mL) under nitrogen. Then stirring and reacting for 3 days in an oil bath at 120 ℃, cooling to room temperature, and distilling off the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by a silica gel chromatographic column, and the leaching agent: the volume ratio of petroleum ether/ethyl acetate was 6:1-3:1, yielding 66mg of product 3-t as a white foamy solid in 76% yield. 1 H NMR(500MHz,DMSO-d 6 ):δ1.42(s,9H),7.28(dd,J＝8.0,4.5Hz,1H),7.32-7.36(m,2H),7.39-7.44(m,2H),7.54-7.57(m,1H),7.60-7.63(m,2H),7.73(d,J＝8.0Hz,1H),7.86(t,J＝2.0Hz,1H),7.94(d,J＝2.0Hz,1H),8.02(dd,J＝5.0,1.5Hz,1H),8.04(t,J＝2.0Hz,1H),8.18(dd,J＝8.0,1.5Hz,1H),8.25(t,J＝2.0Hz,1H),8.31(d,J＝8.0Hz,1H),8.36(dd,J＝4.5,1.5Hz,1H),8.40(d,J＝7.5Hz,1H),8.53(d,J＝8.0Hz,1H),8.65(dd,J＝7.5,1.5Hz,1H),9.05(s,1H). 13 CNMR(126MHz,CDCl 3 ):δ31.23,35.37,109.51,109.98,110.50,116.00,116.30,119.01,119.27,119.76,120.57,120.66,120.72,120.87,121.25,123.13,123.20,123.34,126.43,126.92,128.24,128.26,134.22,135.82,136.18,138.35,140.52,141.07,141.18,142.72,145.07,146.47,152.23,155.18.
(2) Synthesis of Ligand 3: to a tube closure with a magnetic stirrer rotor was added 3-t (152 mg,0.26mmol,1.0 eq.) followed by three nitrogen exchanges and methyl iodide (44 mg,0.31mmol,1.2 eq.) and toluene (4 mL) under nitrogen. Then stirring and reacting for 2 days in an oil bath at 100 ℃, cooling to room temperature, adding petroleum ether (4 mL), filtering after ultrasonic treatment, leaching a filter cake by using petroleum ether, pumping to dry the filter cake, transferring the filter cake into a reaction tube, adding methanol (40 mL) solution, adding water (20 mL) solution of ammonium hexafluorophosphate (56 mg,0.39mmol,1.5 eq.) into the reaction tube, stirring for 3 days at room temperature, removing methanol by reduced pressure distillation, adding water for pumping filtration, leaching the filter cake by using water, and obtaining a crude product. The crude product is separated and purified by a silica gel chromatographic column, and the leaching agent: the volume ratio of dichloromethane/ethyl acetate was 10:1-1:1, yielding 118mg of product Ligand3 as a white powder in 61% yield. 1 H NMR(500MHz,DMSO-d 6 ):δ1.44(s,9H),4.17(s,3H),7.34-7.38(m,2H),7.42-7.48(m,2H),7.57-7.61(m,2H),7.64(dd,J＝8.0,1.5Hz,1H),7.72(d,J＝8.5Hz,1H),7.77(dd,J＝8.0,4.5Hz,1H),7.90(d,J＝1.5Hz,1H),8.01(t,J＝1.5Hz,1H),8.13(dt,J＝8.5,2.0Hz,2H),8.33(d,J＝8.0Hz,1H),8.37(ddd,J＝8.5,4.5,1.5Hz,2H),8.42(d,J＝8.0Hz,1H),8.56(d,J＝8.0Hz,1H),8.63(dd,J＝8.0,1.0Hz,1H),8.67(dd,J＝7.5,1.5Hz,1H),10.45(s,1H). 13 C NMR(126MHz,DMSO-d 6 ):δ30.80,34.01,35.33,108.83,109.95,110.33,115.68,116.55,120.01,120.11,120.34,120.87,120.93,121.02,121.10,121.51,121.54,122.34,122.48,122.83,123.79,124.65,125.18,126.92,127.26,129.00,133.46,134.16,137.37,139.65,140.02,140.39,142.77,144.32,146.33,148.45,151.45,155.10.
(3) Synthesis of PtLS 3: to a tube sealer with a magnetic stirrer rotor, ligand Ligand3 (149 mg,0.20mmol,1.0 eq), (1, 5-cyclooctadiene) platinum dichloride (82 mg,0.22mmol,1.1 eq) and sodium acetate (49 mg,0.60mmol,3.0 eq) were added sequentially, then nitrogen was pumped three times, diethylene glycol dimethyl ether (6 mL) was added under nitrogen protection, and nitrogen bubbling was performed for 30 minutes. Then stirring and reacting for 3 days in an oil bath at 120 ℃, cooling to room temperature, and distilling off the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by a silica gel chromatographic column, and the leaching agent: the volume ratio of petroleum ether/dichloromethane is 5:1-1:1, and the product PtLS3 yellow solid is 26mg, and the yield is 17%. 1 H NMR(500MHz,DMSO-d 6 ):δ1.52(s,9H),3.60(s,3H),7.35(t,J＝7.0Hz,1H),7.42(t,J＝7.0Hz,1H),7.48(dd,J＝8.0,5.0Hz,1H),7.51-7.58(m,2H),7.71-7.74(m,1H),7.88(d,J＝8.0Hz,1H),8.04(d,J＝8.0Hz,1H),8.13-8.17(m,2H),8.28(dd,J＝8.0,1.5Hz,2H),8.35(d,J＝8.5Hz,1H),8.45(d,J＝8.0Hz,1H),8.58(dd,J＝4.5,1.0Hz,1H),8.76(d,J＝1.0Hz,1H),8.99(d,J＝7.5Hz,1H),9.44(dd,J＝5.5,1.0Hz,1H). 13 C NMR(126MHz,CDCl 3 ):δ31.81,34.11,35.28,108.42,110.67,110.76,114.58,115.11,115.61,115.87,116.49,117.42,117.63,118.15,120.08,120.20,121.10,122.04,122.53,124.48,126.33,126.87,127.56,128.39,128.79,136.46,137.11,139.91,140.22,142.51,144.42,145.83,147.47,147.82,149.32,152.71,193.41.
Specific examples of the phosphorescent material of the present invention represented by the following general formula (1) are illustrated below, however, they are not to be construed as limiting the present invention.
Unless otherwise indicated, all commercial reagents referred to in the following experiments were used directly after purchase without further purification. The nuclear magnetic resonance hydrogen spectrum and the carbon spectrum are both in deuterated chloroform (CDCl) 3 ) Or deuterated dimethyl sulfoxide (DMSO-d) 6 ) The hydrogen spectrum is measured by a nuclear magnetic resonance spectrometer of 400 or 500 MHz, the carbon spectrum is measured by a nuclear magnetic resonance spectrometer of 100 or 126 MHz, and the chemical shift is measured by tetramethylsilaneTMS) or residual solvent. If CDCl is used 3 As solvent, the hydrogen and carbon spectra were taken as TMS (delta=0.00 ppm) and CDCl, respectively 3 (δ=77.00 ppm) as an internal standard. If DMSO-d is used 6 As solvent, the hydrogen and carbon spectra were taken as TMS (delta=0.00 ppm) and DMSO-d, respectively 6 (δ=39.52 ppm) as an internal standard. The following abbreviations (or combinations) are used to explain the hydrogen spectrum peaks: s=singlet, d=doublet, t=triplet, q=quartet, p=quintet, m=multiplet, br=broad.
Electrochemical, photophysical test and theoretical calculation description:
the absorbance spectrum was measured on an Agilent 8453 uv-vis spectrometer and steady state emission experiments and lifetime measurements were performed using a Horiba Jobin Yvon FluoroLog-3 spectrometer. The low temperature (77K) emission spectrum and lifetime were measured in a solution of 2-methyltetrahydrofuran (2-MeTHF) cooled with liquid nitrogen.
Experimental data and analysis:
from the photo-emission spectra and photophysical data of PtLS1, ptLS2 and PtLS3 in fig. 1, fig. 2, fig. 3 and table one under different conditions, it can be known that PtLS1, ptLS2 and PtLS3 can be used as sky blue to yellow green phosphorescent materials, and the derived metal complex can have a wider luminescent color by adjusting and controlling substituents on the ligand. As can be seen from the absorption spectra of PtLS1, ptLS2 and PtLS3 in methylene chloride at room temperature in FIG. 4, the absorption peaks at 260nm to 320nm are pi-pi transitions, and the absorption peaks at 330nm to 370nm are metal-to-ligand charge transfer (MLCT).
As can be seen from FIGS. 2 and3, the emission spectra of PtLS1, ptLS2 and PtLS3 in methylene dichloride solution and polymethyl methacrylate film at room temperature are very smooth and have no fine vibration structure, which shows that the charge transfer state (MLCT) component from metal in the excited state of phosphorescent molecules to ligand is more, the service life of the excited state is shortened, and the improvement of the cross-linking rate and the radiation emission rate (k) of phosphorescent molecules is facilitated r obs ) Thereby further improving the quantum efficiency of the molecule. As can be seen from Table one, the excitation states of PtLS1, ptLS2 and PtLS3 are short, and are all about one microsecond, and the radiation emission rate is high, so that the excitation state is all highTo 10 5 s -1 The quantum efficiency of the molecules in the polymethyl methacrylate film reaches 40 percent at the highest. Because of the limited conditions, the test is performed in an air atmosphere, insufficient oxygen is removed, oxygen quenches triplet excitons, experimental data are low, and the measured quantum efficiency is reduced.
Table one: data list of photophysical properties of four-tooth ring metal platinum (II) complex phosphorescent material
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Note that: lambda is the emission wavelength; τ obs The service life of the material in an excited state; phi PL Is phosphorescence quantum efficiency; k (k) r obs Is the rate of radiant emission; wherein k is r obs ＝Φ PL /τ obs . PMMA is polymethyl methacrylate.
The N-heterocyclic carbene ligand in the 5/6/6 parallel ring four-tooth ring metal platinum (II) complex phosphorescent material based on the N-heterocyclic carbene disclosed by the invention is shown in a figure 5, has strong sigma electron donating capability and weak pi electron withdrawing capability, and can form strong coordination bonds and feedback pi bonds from metal to empty p orbitals of carbon atoms in the coordination process of the N-heterocyclic carbene-based 5/6/6 parallel ring four-tooth ring metal platinum (II) complex phosphorescent material. At the same time, the LUMO energy level of the N-heterocyclic carbene ligand molecule is higher, so that the band gap of the molecule is enlarged, and the blue shift of the molecule emission can be realized. The tetradentate ring metal platinum (II) complex molecule has stronger rigidity, can limit the vibration and rotation of the molecule, and reduces non-radiative transition.
In the organic light-emitting element, carriers are injected into a light-emitting material from both positive and negative electrodes, and the light-emitting material in an excited state is generated and emitted. The N-heterocarbene-based 5/6/6-ring-fused four-ring platinum (II) complex represented by the general formula (1) can be used as a phosphorescent light-emitting material in organic photoluminescent elements, organic electroluminescent elements and other excellent organic light-emitting elements. The organic photoluminescent element has a structure in which at least a light-emitting layer is formed on a substrate. The organic electroluminescent element has at least an anode, a cathode, and an organic layer between the anode and the cathode. The organic layer may include at least a light-emitting layer, and may be composed of only a light-emitting layer, or may include 1 or more organic layers other than a light-emitting layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer. The hole transport layer may be a hole injection transport layer having a hole injection function, or the electron transport layer may be an electron injection transport layer having an electron injection function. A schematic structure of a specific organic light emitting element is shown in fig. 6. In fig. 6, a total of 7 layers from bottom to top represent a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode in this order, wherein the light emitting layer is a mixed layer in which a guest material is doped into a host material.
The phosphorescent light-emitting material disclosed by the invention is used as a guest material to be doped into a host material to prepare a light-emitting layer, and can be applied to an OLED device, and the structure is expressed as follows:
ITO/HATCN (10 nm)/TAPC (60 nm)/host material PtLS1 (10 wt.%,35 nm)/PPT (2 nm)/Bepp 2 :Li 2 CO 3 (5wt.％,30nm)/Li 2 CO 3 Al (device structure is not optimized).
Wherein, ITO is a transparent anode; HATCN is hole injection layer, TAPC is hole transport layer, main materials are mCBP and PYD2 respectively, PPT is hole blocking layer, bepp 2 :Li 2 CO 3 Is an electron transport layer, li 2 CO 3 Is an electron injection layer, and Al is a cathode. The numbers in brackets in nanometers (nm) are the thickness of the film.
The molecular formula of the application material in the device is as follows:
and (II) table: list of device performance data with PtLS1 as light emitting material
As can be seen from the accompanying drawings 7, 8 and Table II, the 5/6/6 parallel ring four-toothed ring platinum (II) complex phosphorescent material PtLS1 doped OLED device based on N-heterocarbene is green light, the maximum external quantum efficiency of the device using mCBP and PYD2 as main materials is 13.9% and 13.1%, the maximum emission wavelength is 512nm and 509nm, the starting voltage is 3.5V and 3.9V, and the maximum current efficiency is 42.2cd A -1 And 37.8cd A -1 Maximum power efficiency reaches 29.9lm W respectively -1 And 25.4lm W -1 Most importantly, the maximum brightness of the device is very high and can reach 60276cd m respectively -2 And 64416cd m -2 。
It should be noted that the structure is an example of an application of the phosphorescent material of the present invention, and does not constitute a limitation of a specific OLED device structure of the phosphorescent material of the present invention, and the phosphorescent light emitting material is not limited to the compounds represented in the examples.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples of carrying out the invention and that various changes in form and details may be made therein without departing from the spirit and scope of the invention. For example, many of the substituent structures described herein may be substituted with other structures without departing from the spirit of the invention.
Claims (4)
1. A 5/6/6 parallel ring four-tooth ring metal platinum (II) complex phosphorescent material of N-heterocarbene, characterized in that the structural formula is selected from:
2. use of an N-heterocarbene based 5/6/6-ring tetracyclic platinum (II) complex phosphorescent material according to any one of claims 1 in organic light-emitting elements.
3. The use according to claim 2, wherein the organic light emitting element is a light emitting diode or a light emitting electrochemical cell.
4. The use according to claim 2, wherein the organic light emitting element comprises a first electrode, a second electrode and at least one organic layer arranged between the first electrode and the second electrode; the organic layer comprises a 5/6/6 fused ring four-tooth ring platinum (II) complex based on N-heterocarbene.
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