CN115322227A - Divalent platinum or palladium metal complex phosphorescent material and device based on 8-phenylquinoline and derivative coordination thereof - Google Patents
Divalent platinum or palladium metal complex phosphorescent material and device based on 8-phenylquinoline and derivative coordination thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 75
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 70
- -1 palladium metal complex Chemical class 0.000 title claims abstract description 30
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 22
- WJWVMGIAUYAQLA-UHFFFAOYSA-N 8-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=CC2=CC=CN=C12 WJWVMGIAUYAQLA-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 111
- 239000010410 layer Substances 0.000 claims description 38
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 239000012044 organic layer Substances 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 230000005525 hole transport Effects 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 238000005286 illumination Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000006686 (C1-C24) alkyl group Chemical group 0.000 claims description 2
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- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000004466 alkoxycarbonylamino 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
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 claims description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical class 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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- 150000004696 coordination complex Chemical class 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
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- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 20
- 238000003760 magnetic stirring Methods 0.000 description 19
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 18
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 17
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 17
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 17
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- IIYNXXPDUFXMIA-UHFFFAOYSA-N 3,4,5-trimethyl-2-phenylpyridine Chemical compound CC1=C(C)C(C)=CN=C1C1=CC=CC=C1 IIYNXXPDUFXMIA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-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
-
- 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
- C07F15/006—Palladium compounds
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- 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 provides a divalent platinum or palladium metal complex phosphorescent material and a device based on 8-phenylquinoline and derivative coordination thereof, wherein the divalent platinum and palladium metal complex has a structure shown in a general formula (I):
a novel tetradentate ligand based on 8-phenylquinoline and pyridinol oxygen anion and derivatives thereof is coordinated with a central metal ion to form a 6/5/6 type tetradentate ring metal complex phosphorescent material; in the ligand structure, the steric hindrance between quinoline and phenoxide anions is small, the coordination with central metal is easy, and the formed metalThe complex mother nucleus has good planarity; the material molecule has higher quantum efficiency and high thermal stability, and is suitable to be used as a luminescent material for preparing OLED devices. When the divalent platinum metal complex is applied to an organic light-emitting device, compared with a conventional organic light-emitting device, the current efficiency and the service life of the device are improved.
Description
Technical Field
The invention relates to a divalent platinum or palladium metal complex phosphorescent material based on 8-phenylquinoline and derivative coordination thereof, in particular to a divalent platinum or palladium metal complex, an organic light-emitting device and a display or lighting device, belonging to the field of metal organic photoelectric materials.
Background
Compared with Liquid Crystal Displays (LCDs), organic light emitting devices (e.g., organic light emitting diode devices (OLEDs)) have many advantages such as no need for a backlight source, energy saving, lightness and thinness, colorful color, high color saturation, wide viewing angle, fast response speed, and wide use temperature range, etc. therefore, organic light emitting devices have great application potential in the fields of display and illumination, and thus have received extensive attention from both academic and industrial circles.the design and development of light emitting materials is central to the OLED field.
At present, the heavy metal phosphorescent organic complex molecules which can meet the practical application are basically ring metal trivalent iridium (III)) complex molecules, and the number is limited. The content of the metal platinum element in the earth crust and the annual yield in the world are about ten times of the metal iridium element, and the IrCl used for preparing the trivalent iridium complex phosphorescent material 3 . H 2 The price of O is alsoIs much higher than K for preparing bivalent platinum (II)) complex phosphorescent material 2 PtCl 4 Or PtCl 2 . In addition, the preparation of the trivalent iridium complex phosphorescent material involves three-step reaction of ligand exchange of a trivalent iridium-containing dimer and a trivalent iridium intermediate to generate a mer-iridium (III) complex and isomer conversion from the mer-to fac-iridium (III) complex, so that the total yield is greatly reduced, and the IrCl serving as a raw material is greatly reduced 3 . H 2 The utilization rate of O, thus improving the preparation cost of the trivalent iridium complex phosphorescent material. In contrast, the preparation of the bivalent platinum complex phosphorescent material only has the reaction of the platinum salt designed by the metallization of the ligand in the last step, the utilization rate of the platinum element is high, and the preparation cost of the bivalent platinum complex phosphorescent material can be further reduced. In summary, the preparation cost of the divalent platinum complex phosphorescent material is far lower than that of the trivalent iridium complex phosphorescent material.
The bivalent platinum metal complex based on the bidentate ligand has low molecular rigidity, and two bidentate ligands are easy to twist and vibrate to cause non-radiative decay, so that the phosphorescence quantum efficiency is low (generally less than 30 percent, see Inorganic Chemistry 2002,41,3055-3066.); while a ring bivalent platinum metal complex molecule based on a tridentate ligand requires a second complex anion (e.g. alkyne anion, cl) - Carbenes, etc.), which also results in reduced chemical and thermal stability of the complex. For the above reasons, the application of the phosphorescent material in an OLED device is not favorable. The novel tetradentate ligand is favorable for improving the quantum efficiency and stability of material molecules. Although bivalent platinum or palladium complex phosphorescent materials are reported, bivalent platinum or palladium complex phosphorescent materials capable of meeting the actual use requirements are not reported, and the development of a stable and efficient novel phosphorescent light-emitting material still has great significance for the development of the OLED industry. In order to meet the requirement of three primary colors of full-color display, a red light emitting material with the emission wavelength between 600 and 650nm is necessary, so that a divalent platinum or palladium metal complex light emitting material based on coordination of 8-phenylquinoline and derivatives thereof with a novel structure needs to be developed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a divalent platinum or palladium metal complex phosphorescent material (such as a red light phosphorescent material) based on 8-phenylquinoline and derivative coordination thereof and an organic light-emitting device comprising the same.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a bivalent platinum or palladium metal complex, which has a structure shown in a general formula (I):
wherein:
m is Pt or Pd;
x is O, S or NR;
Y 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 、Y 8 、Y 9 、Y 10 、Y 11 、Y 12 、Y 13 、Y 14 、Y 15 and Y 16 Each independently selected from an N or C atom;
R、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, C1-C24 alkyl, C1-C24 haloalkyl, C1-C24 cycloalkyl, C1-C24 alkoxy, C1-C24 aryl, C1-C24 heteroaryl, C1-C24 aryloxy, halogen, cycloalkenyl, heterocyclyl, alkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, mono-or di-C1-C24 alkylamino, mono-or di-C1-C24 arylamino, ester, nitrile, isonitrile, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, silyl or substituted silyl or a polymeric group, and two or more adjacent R, R 1 、R 2 、R 3 、R 4 And R 5 The rings may be selectively linked to form a ring.
Further, the divalent platinum metal complex has a structure of one of Pt-1 to Pt-649, but is not limited thereto.
The invention also provides an organic light-emitting device which comprises a cathode, an anode and an organic layer, wherein the organic layer at least comprises a light-emitting layer, and the organic layer contains the divalent platinum or palladium metal complex phosphorescent material based on 8-phenylquinoline and derivative coordination thereof.
Further, the organic layer may further include one or more of a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer.
Further, the light-emitting layer also comprises a host material, wherein the volume ratio of the host material to the divalent platinum or palladium metal complex phosphorescent material coordinated based on 8-phenylquinoline and derivatives thereof is 1:99 to 99: the host material is not subject to any limitation.
Further, the organic light emitting device is a full color display, a photovoltaic device, a light emitting display device or an organic light emitting diode.
The present invention also provides a display or illumination apparatus including the organic light emitting device.
The invention has the beneficial effects that: the molecular structure design of the material adopts new 8-phenylquinoline and derivatives thereof to coordinate with central metal ions to form a six-membered metal ring, and simultaneously combines ortho-pyridyl phenol oxygen anions and derivatives thereof to form a novel tetradentate ligand, and the tetradentate ligand coordinates with the central metal ions to form the 6/5/6 type tetradentate ring metal complex phosphorescent material; in the ligand structure, the steric hindrance between quinoline and phenoxide anions is small, the coordination with central metal is easy, and the parent nucleus of the formed metal complex has good planarity; the material molecule has higher quantum efficiency and high thermal stability, and is suitable to be used as a luminescent material for preparing OLED devices. Therefore, the divalent platinum metal complex has certain application value in the fields of OLED display, illumination and the like. When the divalent platinum metal complex is applied to an organic light-emitting device, compared with a conventional organic light-emitting device, the current efficiency of the device is remarkably improved, and meanwhile, the service life of the device is also prolonged.
Drawings
FIG. 1 is a photoluminescence spectrum of compounds Pt-14, pt-124, pt-134, pt-137 and Pt-139 of the present invention in a dichloromethane solution at room temperature;
FIG. 2 is a graph showing photoluminescence spectra of compounds Pt-1, pt-126, pt-183, and Pt-167 according to the present invention in a dichloromethane solution at room temperature;
FIG. 3 is a graph showing photoluminescence spectra of compounds Pt-169, pt-593, pt-592 and Pt-591 according to the present invention in a dichloromethane solution at room temperature;
FIG. 4 is a photoluminescence spectrum of compounds Pt-129, pt-210, pt-144 and Pt-142 of the present invention in a dichloromethane solution at room temperature;
FIG. 5 is a comparison of photoluminescence spectra of compounds Pd-124, pd-210 and Pd-183 of the present invention in a dichloromethane solution at room temperature.
Detailed Description
The present invention will be described in detail below. The following description of the constituent elements may be based on a representative embodiment or specific example of the present invention, but the present invention is not limited to such an embodiment or specific example.
Specific examples of the divalent platinum metal complex (phosphorescent material) of the present invention represented by the following general formula (1) are illustrated below, however, not to be construed as limiting the present invention.
The invention provides an organic light-emitting device, which comprises a first electrode, a second electrode and an organic layer arranged between the first electrode and the second electrode; the organic layer includes a divalent platinum metal complex based on a trimethylphenyl pyridine structural unit.
The invention also provides an application of the bivalent platinum metal complex (phosphorescent material) based on the trimethylphenyl pyridine structural unit in an organic light-emitting device, wherein the organic light-emitting device is an organic light-emitting diode or a light-emitting electrochemical cell.
In particular to application of the divalent platinum metal complex luminescent material containing the quinoline structural unit in serving as a luminescent layer of an organic luminescent device. In an organic light-emitting device, 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 caused to emit light. The compound of the present invention represented by the general formula (1) can be applied as a light-emitting material to an organic light-emitting device such as an organic photoluminescent device or an organic electroluminescent device. The organic photoluminescent device has a structure in which at least a light-emitting layer is formed over a substrate. The organic light-emitting device has a structure in which at least an anode, a cathode, and an organic layer between the anode and the cathode are formed. The organic layer may be composed of only the light-emitting layer, or may have 1 or more organic layers other than the 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, and the electron transport layer may be an electron injection transport layer having an electron injection function.
Examples
Unless otherwise indicated, all commercial reagents referred to in the following examples were purchased and used directly without further purification. The hydrogen spectra of nuclear magnetic resonance are all in deuterated chloroform (CDCl) 3 ) Or deuterated dimethyl sulfoxide (DMSO-d) 6 ) The hydrogen spectra were measured in solution using a 400 or 500 mhz nmr spectrometer. If CDCl is used 3 As solvent, the hydrogen spectrum is CDCl 3 (δ =7.26 ppm) as an internal standard. If DMSO-d is used 6 As solvent, the hydrogen spectrum is DMSO-d 6 (δ =2.50 ppm) as an internal standard. The following abbreviations (or combinations) are used to explain the hydrogen peaks: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad. Optimization of metal complex ground state (S) by using Density Functional Theory (DFT) in theoretical calculation 0 ) The geometry of the molecule; DFT calculations were performed using the B3LYP functional, with C, H, O and N atoms using the 6-31G (d) base group, and Pt and Pd atoms using the LANL2DZ base group.
Example 1: the synthesis route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt-1 is as follows:
synthesis of intermediate (L-1-OMe) to a Schlenk tube with a magnetic stirrer were added 1a (500mg, 1.51mmol,1.0 equiv.), 1b (3970 mg,1.51mmol,1.0 equiv.), tetrakistriphenylphosphine palladium (52mg, 0.045mmol, 3mol%) and potassium carbonate (417mg, 3.02mmol,2.0 equiv.). The nitrogen was then purged three times and 1,4-dioxane (5 mL) and water (1 mL) were added under nitrogen blanket. Reacting in an oil bath at 85 ℃ for 48 hours, cooling to room temperature, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, and eluting: petroleum ether/ethyl acetate =50, giving 470mg of a pale yellow solid, yield 80%. 1 H NMR(500MHz,CDCl 3 )δ3.88(s,3H),7.01(d,J＝8.0Hz,1H),7.09(td,J＝7.5,1.0Hz,1H),7.37(ddd,J＝8.0,7.5,2.0Hz,1H),7.43(dd,J＝8.0,4.0Hz,1H),7.59–7.64(m,2H),7.72(dd,J＝8.0,1.0Hz,1H),7.74–7.78(m,2H),7.81–7.86(m,3H),8.01(dd,J＝7.5,2.0Hz,1H),8.16(dt,J＝8.0,1.5Hz,1H),8.23(dd,J＝8.0,2.0Hz,1H),8.37(t,J＝2.0Hz,1H),8.96(dd,J＝4.0,2.0Hz,1H)。
Synthesis of ligand L-1 to a Schlenk tube with magnetic stirrer was added L-1-OMe (450mg, 1.16mmol,1.0 equiv.), pyridine hydrochloride (1.34g, 11.59mmol,10.0 equiv.). Then the nitrogen was purged three times and 1,3-dimethyl-2-imidazolidinone (4 mL) was added under nitrogen blanket. Reacting in an oil bath kettle at 180 ℃ for 15 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating liquid, drying with anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate =20, 1-5:1, affording 327mg of white solid in 75% yield. 1 H NMR(500MHz,DMSO-d 6 )δ6.92–6.97(m,2H),7.33(ddd,J＝8.5,7.0,1.5Hz,1H),7.60(dd,J＝8.0,4.0Hz,1H),7.70(t,J＝8.0Hz,1H),7.75(dd,J＝8.0,7.0Hz,1H),7.81(dt,J＝8.0,1.0Hz,1H),7.90(dd,J＝7.0,1.5Hz,1H),8.01–8.04(m,2H),8.08(ddd,J＝10.0,8.0,1.5Hz,2H),8.13(t,J＝8.0Hz,1H),8.22(d,J＝8.0Hz,1H),8.28(t,J＝2.0Hz,1H),8.48(dd,J＝8.0,2.0Hz,1H),8.94(dd,J＝4.0,2.0Hz,1H),14.41(s,1H)。
Synthesis of Pt-1 into a three-necked flask with a magnetic stirrer were added L-1 (100mg, 0.27mmol,1.0 eq), potassium tetrachloroplatinate (116mg, 0.28mmol,1.05 eq) and tetrabutylammonium bromide (9mg, 0.027mmol,0.1 eq), nitrogen was purged three times, acetic acid (10 mL) was added under nitrogen protection, and nitrogen was bubbled to remove oxygen for 30min. Putting the three-necked flask into an oil bath kettle with magnetic stirring, stirring at room temperature for 12 hours, heating to 120 ℃ for reaction for 73 hours, cooling the reaction to room temperature, then distilling under reduced pressure to remove the solvent, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =10, 1-1:1, yielding 56mg of a red solid in 37% yield. 1 H NMR(500MHz,DMSO-d 6 )δ6.68(ddd,J＝8.0,6.5,1.5Hz,1H),7.17(dd,J＝8.5,1.5Hz,1H),7.33(ddd,J＝8.5,6.5,2.0Hz,1H),7.40(t,J＝7.5Hz,1H),7.92(t,J＝8.0Hz,1H),7.94–8.01(m,3H),8.14(dd,J＝7.5,1.5Hz,1H),8.19–8.29(m,4H),8.82(dd,J＝8.0,1.0Hz,1H),8.94(dd,J＝8.0,1.5Hz,1H),10.79(dd,J＝5.5,1.5Hz,1H)。
Example 2: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt-126 is as follows:
synthesis of intermediate (L-126-OMe) into a Schlenk tube with a magnetic stirrer were added 2a (500mg, 1.23mmol,1.0 equiv.), 2b (448mg, 1.35mmol,1.1 equiv.), tetrakistriphenylphosphine palladium (43mg, 0.037mmol, 3mol%) and potassium carbonate (340mg, 2.46mmol,2.0 equiv.). The nitrogen was then purged three times and 1,4-dioxane (5 mL) and water (1 mL) were added under nitrogen blanket. Reacting in an oil bath at 100 ℃ for 41 hours, cooling to room temperature, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, eluting: petroleum ether/ethyl acetate =30, to give 610mg of white solid in 86% yield. 1 H NMR(500MHz,CDCl 3 )δ1.33(s,9H),1.45(s,9H),3.42(s,3H),7.34–7.39(m,1H),7.39(d,J＝2.5Hz,1H),7.42–7.49(m,3H),7.64(dd,J＝8.0,7.0Hz,1H),7.71(d,J＝2.5Hz,1H),7.76–7.83(m,5H),7.85–7.89(m,2H),7.99(t,J＝1.5Hz,1H),8.24(dd,J＝8.0,2.0Hz,1H),8.45(d,J＝1.5Hz,2H),8.98(dd,J＝4.0,2.0Hz,1H)。
Synthesis of ligand L-126 to a Schlenk tube with magnetic stirrer was added L-126-OMe (580 mg,1.0mmol,1.0 equiv.), pyridine hydrochloride (1.16g, 10.0mmol,10.0 equiv.). Then the nitrogen was purged three times and 1,3-dimethyl-2-imidazolidinone (3 mL) was added under nitrogen blanket. Reacting in an oil bath at 180 ℃ for 14 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating liquid, drying with anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to remove the solvent. The crude product is separated by a silica gel chromatographic column, and the eluent: petroleum ether/ethyl acetate =20, 1-5:1, yielding 520mg of white solid in 92% yield. 1 H NMR(500MHz,CDCl 3 )δ1.38(s,9H),1.51(s,9H),7.39(tt,J＝7.0,1.0Hz,1H),7.42(d,J＝2.0Hz,1H),7.44–7.51(m,3H),7.67(dd,J＝8.0,7.0Hz,1H),7.72(d,J＝2.5Hz,1H),7.73(dd,J＝6.5,2.0Hz,1H),7.77–7.82(m,2H),7.87–7.94(m,4H),8.05(t,J＝1.5Hz,1H),8.23–8.29(m,2H),8.31(t,J＝1.5Hz,1H),9.05(dd,J＝4.0,2.0Hz,1H),14.94(s,1H)。
Synthesis of Pt-126 to a three-necked flask with a magnetic stirrer were added L-126 (300mg, 0.53mmol,1.0 eq.), potassium tetrachloroplatinate (232mg, 0.56mmol,1.05 eq.) and tetrabutylammonium bromide (17mg, 0.05mmol,0.1 eq.), nitrogen was purged three times, acetic acid (30 mL) was added under nitrogen protection, and nitrogen was bubbled to remove oxygen for 30min. Putting the three-necked flask into an oil bath kettle with magnetic stirring, stirring for 9 hours at room temperature, heating to 120 ℃ for reaction for 79 hours, cooling the reaction to room temperature, then distilling under reduced pressure to remove the solvent, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =10, 1-1:1, yielding 314mg of red solid in 78% yield. 1 H NMR(500MHz,CDCl 3 )δ1.37(s,9H),1.62(s,9H),7.40(tt,J＝7.5,1.5Hz,1H),7.47–7.53(m,3H),7.58–7.63(m,2H),7.72–7.79(m,4H),7.85–7.90(m,2H),7.93–8.01(m,2H),8.16(d,J＝1.0Hz,1H),8.52(dd,J＝8.0,1.5Hz,1H),8.62(dd,J＝8.0,1.5Hz,1H),10.91(dd,J＝5.0,1.5Hz,1H)。
Example 3: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt-183 is as follows:
synthesis of intermediate (L-183-OMe) into a Schlenk tube with a magnetic stirrer were added 3a (500mg, 1.01mmol,1.0 equiv.), 2b (436mg, 1.31mmol,1.3 equiv.), tetrakistriphenylphosphine palladium (58mg, 0.05mmol,5 mol%) and potassium carbonate (279mg, 2.02mmol,2.0 equiv.). The nitrogen was then purged three times and 1,4-dioxane (8 mL) and water (2 mL) were added under nitrogen blanket. Reacting in an oil bath at 100 ℃ for 36 hours, cooling to room temperature, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, and eluting: petroleum ether/ethyl acetate =20, giving 542mg of a pale yellow solid, yield 81%. 1 H NMR(500MHz,CDCl 3 )δ1.30(s,9H),1.44(s,9H),3.41(s,3H),7.30(t,J＝7.5Hz,2H),7.38(d,J＝2.5Hz,1H),7.43–7.49(m,3H),7.63–7.69(m,2H),7.78–7.85(m,5H),7.89(dd,J＝8.0,1.0Hz,1H),7.96(dd,J＝7.0,1.0Hz,1H),8.09(t,J＝1.5Hz,1H),8.16(d,J＝8.0Hz,2H),8.25(dd,J＝8.0,1.5Hz,1H),8.45(t,J＝1.5Hz,1H),8.59(t,J＝1.5Hz,1H),9.04(dd,J＝4.0,1.5Hz,1H)。
Synthesis of ligand L-183-OMe (512mg, 0.78mmol,1.0 equiv.) and pyridine hydrochloride (901mg, 7.80mmol,10.0 equiv.) were added to a Schlenk tube with a magnetic stirrer. Then the nitrogen was purged three times and 1,3-dimethyl-2-imidazolidinone (3 mL) was added under nitrogen blanket. Reacting in an oil bath at 180 ℃ for 19 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating, drying with anhydrous sodium sulfate, filtering, and distilling a filtrate under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate =20, 1-5:1, yielding 430mg of a white solid in 85% yield. 1 H NMR(500MHz,CDCl 3 )δ1.38(s,9H),1.54(s,9H),7.33(ddd,J＝8.0,7.0,1.0Hz,2H),7.44(d,J＝2.0Hz,1H),7.49(dd,J＝8.0,4.0Hz,1H),7.53(ddd,J＝8.5,7.5,1.0Hz,2H),7.68(dd,J＝8.0,7.0Hz,1H),7.70–7.73(m,2H),7.89–7.94(m,5H),7.96(dd,J＝7.0,1.5Hz,1H),8.16–8.20(m,3H),8.24–8.27(m,2H),8.37(t,J＝1.5Hz,1H),9.11(dd,J＝4.0,2.0Hz,1H),14.85(s,1H)。
Synthesis of Pt-183L-183 (200mg, 0.31mmol,1.0 equiv.), potassium tetrachloroplatinate (137mg, 0.33mmol,1.05 equiv.) and tetrabutylammonium bromide (10mg, 0.031mmol,0.1 equiv.) were added to a three-necked flask with a magnetic stirrer, nitrogen gas was purged three times, acetic acid (18 mL) was added under nitrogen gas protection, and oxygen was bubbled with nitrogen gas for 30min. Putting the three-mouth bottle into an oil bath kettle with magnetic stirring, stirring for 8 hours at room temperature, heating to 120 ℃ for reaction for 72 hours, cooling the reaction to room temperature, then removing the solvent by reduced pressure distillation, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =10, 1-1:1, yielding 190mg of red solid in 73% yield. 1 H NMR(500MHz,DMSO-d 6 )δ1.34(s,9H),1.58(s,9H),7.31(ddd,J＝8.0,5.0,3.0Hz,2H),7.42–7.49(m,5H),7.64(d,J＝2.5Hz,1H),7.85(t,J＝8.0Hz,1H),7.97(dd,J＝8.0,5.5Hz,1H),8.17–8.25(m,5H),8.28–8.31(m,3H),8.77(dd,J＝8.0,1.5Hz,1H),9.00(dd,J＝8.0,1.5Hz,1H),10.77(dd,J＝5.5,1.5Hz,1H)。
Example 4: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt-167 is as follows:
synthesis of intermediate (L-167-OMe) into a Schlenk tube with a magnetic stirrer were added 4a (89mg, 0.52mmol,1.1 equiv.), 3b (300mg, 0.47mmol,1.0 equiv.), tetrakistriphenylphosphine palladium (17mg, 0.014mmol,3 mol%) and potassium carbonate (163mg, 1.18mmol,2.5 equiv.). The nitrogen was then purged three times and 1,4-dioxane (6 mL) and water (1 mL) were added under nitrogen blanket. Reacting in an oil bath at 85 ℃ for 36 hours, cooling to room temperature, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, eluting: petroleum ether/ethyl acetate =40, 1-10, yielding 245mg of white solid in 76% yield. 1 H NMR(500MHz,CDCl 3 )δ1.35(s,9H),1.39(s,18H),1.44(s,9H),3.43(s,3H),7.39–7.46(m,2H),7.50–7.55(m,3H),7.64(q,J＝8.0Hz,2H),7.68(d,J＝2.5Hz,1H),7.80(dt,J＝9.0,1.0Hz,1H),7.83–7.86(m,2H),7.92(q,J＝1.5Hz,2H),8.22–8.24(m,2H),8.49(t,J＝3.5Hz,1H),8.97(dd,J＝4.0,2.0Hz,1H)。
Synthesis of ligand L-167 to a Schlenk tube with magnetic stirrer was added L-167-OMe (230mg, 0.33mmol,1.0 equiv.), pyridine hydrochloride (385mg, 3.3mmol,10.0 equiv.). Then the nitrogen was purged three times and 1,3-dimethyl-2-imidazolidinone (3 mL) was added under nitrogen blanket. Reacting in an oil bath at 180 ℃ for 12 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating liquid, drying with anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to remove the solvent. The crude product is separated by a silica gel chromatographic column, and the eluent: petroleum ether/ethyl acetate =100, yielding 210mg of white solid in 94% yield. 1 H NMR(500MHz,CDCl 3 )δ1.36(s,9H),1.41(s,18H),1.51(s,9H),7.43–7.47(m,2H),7.52(d,J＝2.0Hz,2H),7.58(t,J＝3.5Hz,1H),7.65(dd,J＝8.0,7.0Hz,1H),7.70(t,J＝7.7Hz,1H),7.76(d,J＝2.5Hz,1H),7.83–7.88(m,4H),8.00(d,J＝1.5Hz,1H),8.08(dt,J＝8.0,1.5Hz,1H),8.23(dd,J＝8.0,1.5Hz,1H),8.36(t,J＝3.5Hz,1H),9.02(dd,J＝4.0,1.5Hz,1H),14.72(s,1H)。
Synthesis of Pt-167 into a three-necked flask with a magnetic stirrer were added L-167 (150mg, 0.22mmol,1.0 eq), potassium tetrachloroplatinate (101mg, 0.24mmol,1.1 eq) and tetrabutylammonium bromide (8mg, 0.022mmol,0.1 eq), nitrogen was purged three times, acetic acid (14 mL) was added under nitrogen protection, and nitrogen was bubbled to remove oxygen for 30min. Putting the three-necked flask into an oil bath kettle with magnetic stirring, stirring at room temperature for 12 hours, heating to 120 ℃ for reaction for 48 hours, cooling the reaction to room temperature, then distilling under reduced pressure to remove the solvent, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/ethyl acetate =100, 1-4:1, giving 130mg of red solid in 68% yield. 1 H NMR(500MHz,CDCl 3 )δ1.36(s,9H),1.45(s,18H),1.63(s,9H),7.38(t,J＝7.5Hz,1H),7.52(d,J＝2.5Hz,1H),7.60–7.63(m,2H),7.66(d,J＝1.5Hz,2H),7.68(d,J＝2.5Hz,1H),7.75–7.79(m,2H),7.87–7.89(m,2H),8.00(d,J＝8.0Hz,1H),8.13(d,J＝1.5Hz,1H),8.53(dd,J＝8.0,1.5Hz,1H),8.56(d,J＝6.0Hz,1H),10.93(dd,J＝5.5,2.0Hz,1H)。
Example 5: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt-169 is as follows:
synthesis of intermediate (L-169-OMe) to a Schlenk tube with a magnetic stirrer were added 5a (54mg, 0.2mmol,1.0 eq.), 4b (140mg, 0.2mmol,1.0 eq.), tetrakistriphenylphosphine palladium (21mg, 0.018mmol, 9mol%) and potassium carbonate (69mg, 0.5mmol,2.5 eq.). The nitrogen was then purged three times and 1,4-dioxane (5 mL) and water (1 mL) were added under nitrogen blanket. Reacting in an oil bath at 85 ℃ for 24 hours, cooling to room temperature, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, eluting: petroleum ether/ethyl acetate =30, yielding 30mg of white solid in 20% yield. 1 H NMR(500MHz,CDCl 3 )δ1.34(s,9H),1.39(s,18H),1.44(s,9H),1.47(s,9H),3.43(s,3H),7.38–7.41(m,2H),7.53(s,3H),7.65(t,J＝7.5Hz,1H),7.67(d,J＝2.5Hz,1H),7.75(t,J＝2.0Hz,1H),7.80(dt,J＝8.0,1.5Hz,1H),7.91(d,J＝2.5Hz,1H),7.92–7.94(m,2H),8.18(dd,J＝8.5,2.0Hz,1H),8.23(dt,J＝7.5,1.5Hz,1H),8.46(t,J＝3.5Hz,1H),8.90(dd,J＝4.5,2.0Hz,1H)。
Synthesis of ligand L-169 to a Schlenk tube with magnetic stirrer were added L-169-OMe (28mg, 0.038mmol,1.0 eq.) and pyridine hydrochloride (44mg, 0.37mmol,10.0 eq.). Then the nitrogen was purged three times and 1,3-dimethyl-2-imidazolidinone (3 mL) was added under nitrogen blanket. Reacting in an oil bath at 180 ℃ for 12 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating, drying with anhydrous sodium sulfate, filtering, and distilling a filtrate under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate =40, yielding 25mg of white solid in 91% yield. 1 H NMR(500MHz,CDCl 3 )δ1.36(s,9H),1.41(s,18H),1.49(s,9H),1.50(s,9H),7.39–7.43(m,2H),7.53(d,J＝2.0Hz,2H),7.58(t,J＝3.5Hz,1H),7.70(t,J＝7.5Hz,1H),7.77(dd,J＝6.0,2.0Hz,2H),7.84(d,J＝1.5Hz,1H),7.87(dt,J＝7.5,1.0Hz,1H),7.95(d,J＝2.0Hz,1H),8.01(d,J＝1.0Hz,1H),8.06(dt,J＝7.5,1.0Hz,1H),8.19(dd,J＝8.5,2.0Hz,1H),8.34(t,J＝3.0Hz,1H),8.94(dd,J＝4.0,1.5Hz,1H),14.75(s,1H)。
Synthesis of Pt-169L-169 (25mg, 0.034mmol,1.0 equivalent), potassium tetrachloroplatinate (15mg, 0.037mmol,1.1 equivalent) and tetrabutylammonium bromide (1mg, 0.003mmol,0.1 equivalent) were added to a three-necked flask with a magnetic stirrer, nitrogen gas was purged three times, acetic acid (10 mL) was added under nitrogen protection, and oxygen was bubbled with nitrogen gas for 30min. Putting the three-necked flask into an oil bath kettle with magnetic stirring, stirring at room temperature for 12 hours, heating to 120 ℃ for reaction for 48 hours, cooling the reaction to room temperature, then distilling under reduced pressure to remove the solvent, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/ethyl acetate =50, yielding 20mg of a yellow solid in 64% yield. 1 H NMR(500MHz,CDCl 3 ):δ1.36(s,9H),1.44(s,18H),1.53(s,9H),1.63(s,9H),7.39(t,J＝7.5Hz,1H),7.52(d,J＝2.5Hz,1H),7.58(dd,J＝8.0,5.0Hz,1H),7.62(t,J＝3.5Hz,1H),7.66(d,J＝1.5Hz,2H),7.68(d,J＝2.0Hz,1H),7.79(d,J＝8.0Hz,2H),7.87(d,J＝1.5Hz,1H),7.99(d,J＝7.5Hz,1H),8.13(d,J＝1.5Hz,1H),8.49(dd,J＝8.0,1.5Hz,1H),8.64(d,J＝2.0Hz,1H),10.83(dd,J＝5.0,1.5Hz,1H)。
Example 6: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt-593 is as follows:
synthesis of intermediate (L-593-OMe) into a Schlenk tube with magnetic stirrer were added 6a (200mg, 0.36mmol,1.0 equiv.), 4b (122mg, 0.43mmol,1.2 equiv.), tetrakistriphenylphosphine palladium (8mg, 0.007mmol, 2mol%) and potassium carbonate (100mg, 0.72mmol,2.0 equiv.). The nitrogen was then purged three times and 1,4-dioxane (4 mL) and water (1 mL) were added under nitrogen blanket. Reacting in an oil bath at 95 ℃ for 40 hours, cooling to room temperature, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, and eluting: petroleum ether/ethyl acetate =20, 1-5:1 to give 74mg of white solid in 29% yield. 1 H NMR(500MHz,CDCl 3 )δ1.33(s,9H),1.39(s,18H),1.44(s,9H),3.44(s,3H),7.39–7.43(m,2H),7.45(dd,J＝8.0,4.0Hz,1H),7.48–7.54(m,5H),7.64–7.69(m,2H),7.76–7.79(m,2H),7.86(dt,J＝8.0,1.0Hz,1H),7.94(s,2H),8.03(d,J＝2.0Hz,1H),8.12(d,J＝2.0Hz,1H),8.24(dt,J＝8.0,1.5Hz,1H),8.28(dd,J＝8.0,1.5Hz,1H),8.54(t,J＝1.5Hz,1H),8.96(dd,J＝4.0,2.0Hz,1H)。
Synthesis of ligand L-593 to a Schlenk tube with magnetic stirrer was added L-593-OMe (74mg, 0.096mmol,1.0 equiv.), pyridine hydrochloride (111mg, 0.96mmol,10.0 equiv.). Then the nitrogen was purged three times and 1,3-dimethyl-2-imidazolidinone (1 mL) was added under nitrogen blanket. Reacting in an oil bath kettle at 180 ℃ for 9 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating, drying with anhydrous sodium sulfate, filtering, and distilling a filtrate under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate =30, 1-5:1, giving 66mg of white solid, 91% yield. 1 H NMR(500MHz,CDCl 3 )δ1.36(s,9H),1.41(s,18H),1.50(s,9H),7.40–7.43(m,2H),7.47(dd,J＝8.0,4.0Hz,1H),7.49–7.54(m,4H),7.58(t,J＝2.0Hz,1H),7.73(d,J＝8.0Hz,1H),7.76(d,J＝2.5Hz,1H),7.78–7.81(m,2H),7.85(d,J＝1.5Hz,1H),7.91(dt,J＝7.5,1.0Hz,1H),8.01(d,J＝1.5Hz,1H),8.05(d,J＝2.5Hz,1H),8.09(dt,J＝8.0,1.5Hz,1H),8.13(d,J＝2.0Hz,1H),8.29(dd,J＝8.0,1.5Hz,1H),8.41(t,J＝1.5Hz,1H),9.01(dd,J＝4.0,2.0Hz,1H),14.72(s,1H)。
Synthesis of Pt-593 into a three-necked flask equipped with a magnetic stirrer were charged L-593 (63mg, 0.084mmol,1.0 eq.), potassium tetrachloroplatinate (37mg, 0.088mmol,1.05 eq.) and tetrabutylammonium bromide (3mg, 0.008mmol,0.1 eq.), nitrogen gas was purged three times, acetic acid (5 mL) was added under nitrogen protection, and oxygen was bubbled with nitrogen gas for 30min. Putting the three-mouth bottle into an oil bath kettle with magnetic stirring, stirring for 12 hours at room temperature, heating to 120 ℃ for reaction for 48 hours, cooling the reaction to room temperature, then removing the solvent by reduced pressure distillation, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =10, 1-1:1, yielding 54mg of a yellow solid in 68% yield. 1 H NMR(500MHz,CDCl 3 )δ1.37(s,9H),1.45(s,18H),1.64(s,9H),7.39(t,J＝7.5Hz,1H),7.46–7.50(m,1H),7.53(d,J＝2.5Hz,1H),7.55–7.58(m,2H),7.62–7.67(m,4H),7.69(d,J＝2.5Hz,1H),7.79–7.84(m,3H),7.88(d,J＝1.5Hz,1H),8.05(d,J＝2.0Hz,1H),8.07(d,J＝8.0Hz,1H),8.14(d,J＝1.5Hz,1H),8.57(dd,J＝8.0,1.5Hz,1H),8.79(d,J＝2.0Hz,1H),10.91(dd,J＝5.5,1.5Hz,1H)。
Example 7: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt-14 is as follows:
synthesis of intermediate (L-14-OMe) to a Schlenk tube with a magnetic stirrer were added 7a (800mg, 2.07mmol,1.0 equiv.), 1b (543mg, 2.07mmol,1.0 equiv.), tetrakistriphenylphosphine palladium (48mg, 0.041mmol, 2mol%) and potassium carbonate (572mg, 4.14mmol,2.0 equiv). The nitrogen was then purged three times and 1,4-dioxane (6 mL) and water (1 mL) were added under nitrogen blanket. Reacting in an oil bath at 85 ℃ for 34 hours, cooling to room temperature, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, eluting: petroleum ether/ethyl acetate =50, to give 803mg of a brown solid in 87% yield. 1 H NMR(500MHz,CDCl 3 )δ1.47(s,9H),3.89(s,3H),7.01(dd,J＝8.5,1.0Hz,1H),7.08(td,J＝7.5,1.0Hz,1H),7.34–7.41(m,2H),7.61(t,J＝7.5Hz,1H),7.72(dd,J＝8.0,1.0Hz,1H),7.74–7.78(m,3H),7.85(dd,J＝7.5,1.0Hz,1H),7.89(d,J＝2.0Hz,1H),8.03(dd,J＝7.5,1.5Hz,1H),8.15(ddd,J＝7.5,2.0,1.0Hz,1H),8.18(dd,J＝8.0,2.0Hz,1H),8.37(t,J＝1.5Hz,1H),8.90(dd,J＝4.0,2.0Hz,1H)。
Synthesis of ligand L-14 to a Schlenk tube with a magnetic stirrer were added L-14-OMe (750mg, 1.69mmol,1.0 equiv.), pyridine hydrochloride (1.95g, 16.87mmol,10.0 equiv.). Then the nitrogen was purged three times and 1,3-dimethyl-2-imidazolidinone (4 mL) was added under nitrogen blanket. Reacting in an oil bath at 180 ℃ for 28 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating, drying with anhydrous sodium sulfate, filtering, and distilling a filtrate under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate =50, to give623mg of white solid, yield 86%. 1 H NMR(500MHz,DMSO-d 6 )δ1.47(s,10H),6.90–6.98(m,2H),7.30–7.35(m,1H),7.56(ddd,J＝8.0,4.0,1.0Hz,1H),7.70(t,J＝7.5Hz,1H),7.82–7.85(m,1H),7.97(s,2H),8.02(d,J＝7.5Hz,2H),8.09(dt,J＝8.0,1.5Hz,1H),8.14(td,J＝8.0,1.0Hz,1H),8.22(d,J＝8.0Hz,1H),8.28(q,J＝1.5Hz,1H),8.44(dt,J＝8.0,1.5Hz,1H),8.86(dd,J＝4.0,2.0Hz,1H),14.47(s,1H)。
Synthesis of Pt-14 into a three-necked flask with a magnetic stirrer were added L-14 (300mg, 0.70mmol,1.0 equiv.), potassium tetrachloroplatinate (304mg, 0.73mmol,1.05 equiv.), and tetrabutylammonium bromide (23mg, 0.07mmol,0.1 equiv.), nitrogen was purged three times, acetic acid (42 mL) was added under nitrogen protection, and oxygen was bubbled with nitrogen for 30min. Putting the three-necked flask into an oil bath kettle with magnetic stirring, stirring for 13 hours at room temperature, heating to 120 ℃ for reaction for 62 hours, cooling the reaction to room temperature, then distilling under reduced pressure to remove the solvent, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =10, 1-1:1, giving 363mg of a reddish-brown solid in 83% yield. 1 H NMR(500MHz,DMSO-d 6 )δ1.52(s,9H),6.68(ddd,J＝8.0,6.5,1.5Hz,1H),7.16(dd,J＝8.5,1.5Hz,1H),7.32(ddd,J＝8.5,6.5,1.5Hz,1H),7.41(t,J＝7.5Hz,1H),7.92(dd,J＝8.0,5.5Hz,1H),7.96(d,J＝7.5Hz,1H),7.98(dd,J＝8.5,1.5Hz,1H),8.13–8.15(m,2H),8.20–8.27(m,3H),8.78(d,J＝2.0Hz,1H),8.91(dd,J＝8.0,1.5Hz,1H),10.71(dd,J＝5.5,1.5Hz,1H)。
Example 8: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt-124 is as follows:
synthesis of intermediate (L-124-OMe) into a Schlenk tube with a magnetic stirrer were added 7a (600mg, 1.55mmol,1.0 eq), 5b (613mg, 1.63mmol,1.05 eq), tetrakistriphenylphosphine palladium (36mg, 0.031mmol, 2mol%) and potassium carbonate (428mg, 3.10mmol,2.0 eq). The nitrogen was then purged three times and 1,4-dioxane (5 mL) and water (1 mL) were added under nitrogen blanket. 100 ℃ oil bath in the panAfter a further 20 hours, the mixture is cooled to room temperature, the solvent is removed by distillation under reduced pressure and the crude product is separated on a silica gel column, eluent: petroleum ether/ethyl acetate =30, 1-5:1, yielding 735mg of white solid in 85% yield. 1 H NMR(500MHz,CDCl 3 )δ1.32(s,9H),1.44(s,9H),1.47(s,9H),3.39(s,3H),7.37–7.40(m,2H),7.61–7.64(m,2H),7.72–7.79(m,5H),7.89(d,J＝2.0Hz,1H),8.16–8.19(m,2H),8.44(t,J＝2.0Hz,1H),8.90(dd,J＝4.0,2.0Hz,1H)。
Synthesis of ligand L-124 to a Schlenk tube with magnetic stirrer was added L-124-OMe (700mg, 1.26mmol,1.0 eq.), pyridine hydrochloride (1.45g, 12.57mmol,10.0 eq.). Then the nitrogen was purged three times and 1,3-dimethyl-2-imidazolidinone (3 mL) was added under nitrogen blanket. Reacting in an oil bath at 180 ℃ for 19 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating, drying with anhydrous sodium sulfate, filtering, and distilling a filtrate under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate =50, 1-10, giving 621mg of white solid in 91% yield. 1 H NMR(500MHz,DMSO-d 6 )δ1.33(s,9H),1.41(s,9H),1.46(s,9H),7.33(d,J＝2.5Hz,1H),7.55(dd,J＝8.0,4.0Hz,1H),7.71(t,J＝7.5Hz,1H),7.84(d,J＝2.5Hz,1H),7.85(dt,J＝7.5,1.0Hz,1H),7.95–7.97(m,2H),8.01–8.06(m,2H),8.12(t,J＝8.0Hz,1H),8.23–8.25(m,1H),8.27(t,J＝2.0Hz,1H),8.43(dd,J＝8.0,1.5Hz,1H),8.88(dd,J＝4.0,2.0Hz,1H),15.08(s,1H)。
Synthesis of Pt-124 to a three-necked flask with a magnetic stirrer, L-124 (300mg, 0.55mmol,1.0 equiv.), potassium tetrachloroplatinate (241mg, 0.58mmol,1.05 equiv.) and tetrabutylammonium bromide (19mg, 0.06mmol,0.1 equiv.) were added, nitrogen was purged three times, acetic acid (35 mL) was added under nitrogen, and nitrogen was bubbled to remove oxygen for 30min. Putting the three-necked flask into an oil bath kettle with magnetic stirring, stirring at room temperature for 12 hours, heating to 120 ℃ for reaction for 72 hours, cooling the reaction to room temperature, then distilling under reduced pressure to remove the solvent, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =10, 1-1:1, giving 347mg of a tan solid in 86% yield. 1 H NMR(500MHz,CDCl 3 )δ1.36(s,9H),1.52(s,9H),1.60(s,9H),7.36(t,J＝7.5Hz,1H),7.50(d,J＝2.5Hz,1H),7.56–7.58(m,2H),7.68(d,J＝7.5Hz,2H),7.78(d,J＝2.0Hz,1H),7.91–7.98(m,3H),8.48(dd,J＝8.0,1.5Hz,1H),8.62(d,J＝2.0Hz,1H),10.80(dd,J＝5.5,1.5Hz,1H)。
Example 9: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt-139 is as follows:
synthesis of intermediate (L-139-OMe) 7a (900mg, 2.32mmol,1.0 equiv.), 6b (767mg, 2.44mmol,1.05 equiv.), tetrakistriphenylphosphine palladium (54mg, 0.046mmol,2 mol%) and potassium carbonate (641mg, 4.64mmol,2.0 equiv.) were added to a Schlenk tube with a magnetic stirrer. The nitrogen was then purged three times and 1,4-dioxane (8 mL) and water (2 mL) were added under nitrogen blanket. Reacting in an oil bath kettle at 90 ℃ for 60 hours, cooling to room temperature, removing the solvent by reduced pressure distillation, separating the crude product by using a silica gel chromatographic column, and eluting: petroleum ether/ethyl acetate =30, 1.09g of white solid was obtained with a yield of 95%. 1 H NMR(500MHz,CDCl 3 )δ1.44(s,9H),3.87(s,3H),7.29–7.35(m,2H),7.38(dd,J＝8.5,4.0Hz,2H),7.41(dd,J＝7.5,1.0Hz,1H),7.57(t,J＝7.5Hz,1H),7.63–7.67(m,1H),7.72–7.75(m,2H),7.79–7.92(m,5H),8.11(ddd,J＝7.5,2.0,1.0Hz,1H),8.16(dd,J＝8.0,1.5Hz,1H),8.33(t,J＝1.5Hz,1H),8.88(dd,J＝4.0,2.0Hz,1H)。
Synthesis of ligand L-139 to a Schlenk tube with magnetic stirrer was added L-139-OMe (1.0 g,2.01mmol,1.0 equiv.), pyridine hydrochloride (2.33g, 20.14mmol,10.0 equiv.). Then the nitrogen was purged three times and 1,3-dimethyl-2-imidazolidinone (3 mL) was added under nitrogen blanket. Reacting in an oil bath kettle at 180 ℃ for 24 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating liquid, drying with anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to remove the solvent. The crude product is separated by a silica gel chromatographic column, and the eluent: petroleum ether/ethyl acetate =50, yielding 847mg of white solid in 88% yield. 1 H NMR(500MHz,DMSO-d 6 )δ1.42(s,9H),7.24–7.33(m,3H),7.50–7.54(m,2H),7.57–7.61(m,2H),7.70(dt,J＝7.5,1.5Hz,1H),7.82–7.86(m,2H),7.89(d,J＝2.0Hz,1H),7.92(d,J＝2.5Hz,1H),8.02(d,J＝1.5Hz,1H),8.03(s,1H),8.10(dt,J＝8.0,1.5Hz,1H),8.30(t,J＝1.5Hz,1H),8.40(dd,J＝8.5,1.5Hz,1H),8.83(dd,J＝4.0,2.0Hz,1H),10.11(s,1H)。
Synthesis of Pt-139 into a three-necked flask equipped with a magnetic stirrer were charged L-139 (300mg, 0.62mmol,1.0 equiv.), potassium tetrachloroplatinate (272mg, 0.66mmol,1.05 equiv.), and tetrabutylammonium bromide (20mg, 0.06mmol,0.1 equiv.), nitrogen gas was purged three times, acetic acid (40 mL) was added under nitrogen gas protection, and nitrogen gas was bubbled to remove oxygen for 30min. Putting the three-mouth bottle into an oil bath kettle with magnetic stirring, stirring for 13 hours at room temperature, heating to 120 ℃ for reaction for 56 hours, cooling the reaction to room temperature, then carrying out reduced pressure distillation to remove the solvent, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =10, 1-1:1, yielding 371mg of an orange-yellow solid in 89% yield. 1 H NMR(500MHz,DMSO-d 6 )δ1.52(s,9H),7.18(ddd,J＝8.0,7.0,1.0Hz,1H),7.36(ddd,J＝8.5,7.0,1.5Hz,1H),7.39(d,J＝9.0Hz,1H),7.44(t,J＝7.5Hz,1H),7.78(dd,J＝8.0,1.0Hz,1H),7.81(d,J＝9.0Hz,1H),7.89–7.98(m,4H),8.09(dd,J＝8.0,1.0Hz,1H),8.13–8.19(m,2H),8.21(d,J＝8.0Hz,1H),8.77(d,J＝2.0Hz,1H),8.92(dd,J＝8.5,1.5Hz,1H),10.66(dd,J＝5.5,1.5Hz,1H)。
Example 10: the synthesis route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt-137 is as follows:
synthesis of intermediate (L-137-OMe) into a Schlenk tube with a magnetic stirrer were added 7a (600mg, 1.55mmol,1.0 equiv.), 7b (511mg, 1.63mmol,1.05 equiv.), tetrakistriphenylphosphine palladium (36mg, 0.031mmol, 2mol%) and potassium carbonate (428mg, 3.10mmol,2.0 equiv.). The nitrogen was then purged three times and 1,4-dioxane (5 mL) and water (1 mL) were added under nitrogen blanket. Reacting in oil bath at 100 deg.C for 47 hr, cooling to room temperature, distilling under reduced pressure to remove solvent, and performing silica gel chromatographyColumn separation, eluent: petroleum ether/ethyl acetate =30 to give 693mg of white solid in 90% yield. 1 H NMR(500MHz,CDCl 3 )δ1.48(s,9H),3.78(s,3H),7.41(dd,J＝8.0,4.0Hz,1H),7.50–7.57(m,2H),7.64(t,J＝7.5Hz,1H),7.71(d,J＝8.5Hz,1H),7.76–7.80(m,3H),7.83–7.88(m,2H),7.91(d,J＝2.0Hz,1H),8.08(d,J＝7.5Hz,1H),8.17(d,J＝8.5Hz,1H),8.18–8.22(m,2H),8.26(dd,J＝8.0,1.5Hz,1H),8.44(t,J＝1.5Hz,1H),8.91(dd,J＝4.0,2.0Hz,1H)。
Synthesis of ligand L-137 into a Schlenk tube with magnetic stirrer were added L-137-OMe (670mg, 1.35mmol,1.0 equiv.), pyridine hydrochloride (1.57g, 13.55mmol,10.0 equiv.). Then the nitrogen was purged three times and 1,3-dimethyl-2-imidazolidinone (3 mL) was added under nitrogen blanket. Reacting in an oil bath at 180 ℃ for 16 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating liquid, drying with anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate =50 to give 588mg of light yellow solid in 91% yield. 1 H NMR(500MHz,DMSO-d 6 )δ1.50(s,9H),7.47(d,J＝8.5Hz,1H),7.52(ddd,J＝8.0,6.5,1.5Hz,1H),7.56–7.59(m,2H),7.74(t,J＝7.5Hz,1H),7.88(d,J＝8.0Hz,1H),7.91(dt,J＝7.5,1.5Hz,1H),7.99(d,J＝2.5Hz,1H),8.03–8.05(m,2H),8.08(ddd,J＝7.5,2.0,1.0Hz,1H),8.15–8.21(m,2H),8.30–8.34(m,2H),8.35(t,J＝1.5Hz,1H),8.45(dd,J＝8.0,1.5Hz,1H),8.91(dd,J＝4.0,2.0Hz,1H),16.39(s,1H)。
Synthesis of Pt-137 into a three-necked flask equipped with a magnetic stirrer were charged L-137 (300mg, 0.62mmol,1.0 equiv.), potassium tetrachloroplatinate (272mg, 0.66mmol,1.05 equiv.), and tetrabutylammonium bromide (20mg, 0.06mmol,0.1 equiv.), nitrogen gas was purged three times, acetic acid (40 mL) was added under nitrogen gas protection, and oxygen was bubbled with nitrogen gas for 30min. Putting the three-mouth bottle into an oil bath kettle with magnetic stirring, stirring for 12 hours at room temperature, heating to 120 ℃ for reaction for 58 hours, cooling the reaction to room temperature, then removing the solvent by reduced pressure distillation, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane = 10-1:1 to give 152mg of a tan solid in 36% yield. 1 H NMR(500MHz,CDCl 3 )δ1.54(s,9H),7.12(d,J＝9.0Hz,1H),7.38(t,J＝7.5Hz,1H),7.49–7.57(m,2H),7.68(dd,J＝7.5,1.5Hz,1H),7.69–7.75(m,3H),7.79(d,J＝2.0Hz,1H),7.88(d,J＝9.0Hz,1H),7.95–8.0(m,1H),8.03(d,J＝8.0Hz,2H),8.50(dd,J＝8.0,1.5Hz,1H),8.68(d,J＝2.0Hz,1H),8.79–8.82(m,1H),10.98(dd,J＝5.5,1.5Hz,1H)。
Example 11: the synthesis route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt-134 is as follows:
synthesis of intermediate (L-134-OMe) to a Schlenk tube with a magnetic stirrer were added 7a (600mg, 1.55mmol,1.0 eq), 8b (553mg, 1.63mmol,1.05 eq), tetrakistriphenylphosphine palladium (61mg, 0.046mmol, 3mol%) and potassium carbonate (610mg, 3.87mmol,2.5 eq). The nitrogen was then purged three times and 1,4-dioxane (8 mL) and water (2 mL) were added under nitrogen blanket. Reacting in an oil bath at 85 ℃ for 48 hours, cooling to room temperature, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, and eluting: petroleum ether/ethyl acetate =10, yielding 730mg of white solid in 80% yield. 1 H NMR(500MHz,CDCl 3 )δ1.44(s,9H),3.93(s,3H),7.09(d,J＝8.5Hz,1H),7.28–7.31(m,1H),7.35–7.40(m,3H),7.59–7.63(m,4H),7.74–7.76(m,3H),7.79(dd,J＝10.5Hz,1H),7.85(dd,J＝8.0,1.5Hz,1H),7.87(d,J＝2.5Hz,1H),8.14–8.18(m,2H),8.24(d,J＝2.5Hz,1H),8.41(t,J＝3.0Hz,1H),8.86(dd,J＝4.0,1.5Hz,1H)。
Synthesis of ligand L-134 to a Schlenk tube with magnetic stirrer were added L-134-OMe (710mg, 1.36mmol,1.0 equiv.), pyridine hydrochloride (1.58g, 13.6mmol,10.0 equiv.). Then the nitrogen was purged three times and 1,3-dimethyl-2-imidazolidinone (4 mL) was added under nitrogen blanket. Reacting in an oil bath at 180 ℃ for 12 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating liquid, drying with anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum productsEther/ethyl acetate =5:1 to give 550mg of white solid in 94% yield. 1 H NMR(500MHz,CDCl 3 )δ1.50(s,9H),7.11(d,J＝8.5Hz,1H),7.32–7.35(m,1H),7.41(dd,J＝8.0,4.0Hz,1H),7.44–7.47(m,2H),7.56(dd,J＝8.5,2.0Hz,1H),7.60–7.63(m,2H),7.68(t,J＝7.5Hz,1H),7.74(dd,J＝6.0,1.0Hz,1H),7.79(d,J＝2.0Hz,1H),7.84(dt,J＝8.0,1.5Hz,1H),7.91–7.98(m,3H),8.02(ddd,J＝7.5,2.0,1.5Hz,1H),8.07(d,J＝2.0Hz,1H),8.20(dd,J＝8.5,2.0Hz,1H),8.28(t,J＝3.5Hz,1H),8.92(dd,J＝4.0,1.5Hz,1H),14.82(s,1H)。
Synthesis of Pt-134 to a three-necked flask equipped with a magnetic stirrer were added L-134 (300mg, 0.59mmol,1.0 eq), potassium tetrachloroplatinate (257mg, 0.62mmol,1.05 eq), and tetrabutylammonium bromide (19mg, 0.06mmol,0.1 eq), nitrogen gas was purged three times, acetic acid (35 mL) was added under nitrogen protection, and nitrogen gas was bubbled to remove oxygen for 30min. Putting the three-mouth bottle into an oil bath kettle with magnetic stirring, stirring for 12 hours at room temperature, heating to 120 ℃ for reaction for 62 hours, cooling the reaction to room temperature, then removing the solvent by reduced pressure distillation, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =10, 1-1:1 to give 318mg orange yellow solid, 77% yield. 1 H NMR(500MHz,DMSO-d 6 )δ1.52(s,9H),7.25–7.29(m,2H),7.41–7.45(m,3H),7.68(dd,J＝8.5,2.5Hz,1H),7.72–7.74(m,2H),7.93(dd,J＝8.5,5.5Hz,1H),7.97(d,J＝8.0Hz,1H),8.15–8.17(m,2H),8.20(d,J＝2.5Hz,1H),8.25(t,J＝7.0Hz,2H),8.43(d,J＝8.5Hz,1H),8.78(d,J＝2.5Hz,1H),8.92(dd,J＝8.5,2.0Hz,1H),10.70(d,J＝5.5,2.0Hz,1H)。
Example 12: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt-129 is as follows:
synthesis of intermediate (L-129-OMe) into a Schlenk tube with a magnetic stirrer were added 8a (443mg, 1.0mmol,1.0 equiv.), 2b (332mg, 1.0mmol,1.0 equiv.), tetrakistriphenylphosphine palladium (35mg, 0.03mmol, 3mol%) and potassium carbonate (276mg, 2.0mmol,2.0 equiv.). Then the nitrogen is pumped and changedThe gas was purged three times and 1,4-dioxane (4 mL) and water (1 mL) were added under nitrogen blanket. Reacting in an oil bath at 100 ℃ for 34 hours, cooling to room temperature, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, and eluting: petroleum ether/ethyl acetate =30, and 457mg of a white solid was obtained in 75% yield. 1 H NMR(500MHz,CDCl 3 )δ1.33(s,9H),1.45(s,9H),1.47(s,9H),1.47(s,9H),3.42(s,3H),7.37–7.40(m,2H),7.72–7.79(m,6H),7.88(d,J＝2.5Hz,1H),8.18(dd,J＝8.0,2.0Hz,1H),8.22(t,J＝1.5Hz,1H),8.27(t,J＝1.5Hz,1H),8.89(dd,J＝4.0,2.0Hz,1H)。
Synthesis of ligand L-129 to a Schlenk tube with magnetic stirrer was added L-129-OMe (424mg, 0.69mmol,1.0 equiv.), pyridine hydrochloride (799mg, 6.92mmol,10.0 equiv.). Then the nitrogen was purged three times and 1,3-dimethyl-2-imidazolidinone (3 mL) was added under nitrogen blanket. Reacting in an oil bath at 180 ℃ for 17 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating liquid, drying with anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate =50, 1-10, yielding 392mg of a yellow solid in 95% yield. 1 H NMR(500MHz,CDCl 3 )δ1.37(s,9H),1.49(s,9H),1.50(s,18H),7.39–7.42(m,2H),7.65–7.69(m,1H),7.72(d,J＝2.5Hz,1H),7.78(d,J＝2.5Hz,1H),7.85(t,J＝1.5Hz,1H),7.87–7.89(m,2H),7.93(d,J＝2.0Hz,1H),8.08–8.11(m,2H),8.19(dd,J＝8.0,2.0Hz,1H),8.94(dd,J＝4.0,2.0Hz,1H),15.09(s,1H)。
Synthesis of Pt-129 to a three-necked flask with a magnetic stirrer were added L-129 (250mg, 0.42mmol,1.0 eq), potassium tetrachloroplatinate (182mg, 0.44mmol,1.05 eq) and tetrabutylammonium bromide (14mg, 0.042mmol,0.1 eq), nitrogen was purged three times, acetic acid (25 mL) was added under nitrogen protection, and nitrogen was bubbled to remove oxygen for 30min. Putting the three-necked flask into an oil bath kettle with magnetic stirring, stirring at room temperature for 12 hours, heating to 120 ℃ for reaction for 72 hours, cooling the reaction to room temperature, then distilling under reduced pressure to remove the solvent, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =10, 1-1:1, yielding 170mg of a tan solid in 51% yield. 1 H NMR(500MHz,CDCl 3 )δ1.36(s,9H),1.49(s,9H),1.53(s,9H),1.61(s,9H),7.50(d,J＝2.5Hz,1H),7.56(dd,J＝8.0,5.5Hz,1H),7.59(d,J＝2.5Hz,1H),7.71–7.73(m,2H),7.77(d,J＝2.0Hz,1H),7.90–7.98(m,2H),8.01(d,J＝1.0Hz,1H),8.47(dd,J＝8.0,1.5Hz,1H),8.62(d,J＝2.0Hz,1H),10.79(dd,J＝5.5,2.0Hz,1H)。
Example 13: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt-210 is as follows:
synthesis of intermediate (L-210-OMe) to a Schlenk tube with a magnetic stirrer were added 8a (410mg, 0.92mmol,1.05 equiv.), 8b (300mg, 0.88mmol,1.00 equiv.), tetrakistriphenylphosphine palladium (30mg, 0.026mmol, 3mol%) and potassium carbonate (304mg, 2.2mmol,2.5 equiv.). The nitrogen was then purged three times and 1,4-dioxane (6 mL) and water (2 mL) were added under nitrogen blanket. Reacting in an oil bath at 85 ℃ for 48 hours, cooling to room temperature, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, and eluting: petroleum ether/ethyl acetate =50, 1-10, yielding 450mg of white solid in 88% yield. 1 H NMR(500MHz,CDCl 3 )δ1.45(s,9H),1.48(s,9H),3.94(s,3H),7.09(d,J＝4.0Hz,1H),7.28–7.31(m,1H),7.34–7.41(m,3H),7.61–7.65(m,3H),7.72–7.74(m,2H),7.77–7.80(m,2H),7.87(d,J＝6.0Hz,1H),7.90(dd,J＝7.5,1.0Hz,1H),8.17(dd,J＝8.0,1.5Hz,1H),8.20(t,J＝3.5Hz,2H),8.39(d,J＝2.5Hz,1H),8.85(dd,J＝4.0,2.0Hz,1H)。
Synthesis of ligand L-210 to a Schlenk tube with magnetic stirrer was added L-210-OMe (430mg, 0.75mmol,1.0 equiv.), pyridine hydrochloride (861mg, 7.5mmol,10.0 equiv.). Then the nitrogen was purged three times and 1,3-dimethyl-2-imidazolidinone (3 mL) was added under nitrogen blanket. Reacting in an oil bath at 180 ℃ for 12 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating liquid, drying with anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to remove the solvent. The crude product is separated by a silica gel chromatographic column, and the eluent: petroleum ether/acetic acid ethyl esterEster =10, yielding 300mg of white solid in 72% yield. 1 H NMR(500MHz,CDCl 3 )δ1.50(s,9H),1.50(s,9H),7.12(d,J＝8.0Hz,1H),7.32–7.35(m,1H),7.41(d,J＝8.5,4.5Hz,1H),7.44–7.47(m,2H),7.56(dd,J＝8.5,2.0Hz,1H),7.61–7.63(m,2H),7.74(dd,J＝7.5,1.5Hz,1H),7.78(d,J＝2.5Hz,1H),7.85(t,J＝3.5Hz,1H),7.91–7.97(m,3H),8.07(t,J＝3.5Hz,2H),8.09(t,J＝3.5Hz,1H),8.20(dd,J＝8.5,2.0Hz,1H),8.92(dd,J＝4.0,1.5Hz,1H),14.78(s,1H)。
Synthesis of Pt-210 into a three-necked flask with a magnetic stirrer were added L-210 (200mg, 0.36mmol,1.0 equiv.), potassium tetrachloroplatinate (162mg, 0.400mmol,1.1 equiv.) and tetrabutylammonium bromide (111mg, 0.036mmol,0.1 equiv.), nitrogen was purged three times, acetic acid (15 mL) was added under nitrogen protection, and nitrogen was bubbled to remove oxygen for 30min. Putting the three-mouth bottle into an oil bath kettle with magnetic stirring, stirring for 12 hours at room temperature, heating to 120 ℃ for reaction for 48 hours, cooling the reaction to room temperature, then removing the solvent by reduced pressure distillation, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =10, yielding 205mg of yellow solid in 76% yield. 1 H NMR(500MHz,DMSO-d 6 )δ1.49(s,9H),1.54(s,9H),7.24–7.29(m,2H),7.44(t,J＝7.5Hz,2H),7.68(dd,J＝8.5,2.0Hz,1H),7.74(dd,J＝8.5,1.5Hz,2H),7.94(dd,J＝8.0,5.5Hz,1H),8.02(d,J＝1.5Hz,1H),8.08(d,J＝1.0Hz,1H),8.17(d,J＝2.0Hz,1H),8.20(d,J＝2.5Hz,1H),8.24(t,J＝7.0Hz,1H),8.30–8.31(m,1H),8.42–8.44(m,1H),8.73(d,J＝2.5Hz,1H),8.94(dd,J＝8.5,1.5Hz,1H),10.69(dd,J＝5.5,2.0Hz,1H)。
Example 14: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt-144 is as follows:
synthesis of intermediate (L-144-OMe) into a Schlenk tube with a magnetic stirrer were added 8a (590mg, 1.33mmol,1.05 equiv.), 6b (400mg, 1.27mmol,1.0 equiv.), tetrakistriphenylphosphine palladium (44mg, 0.038mmol, 3mol%) and potassium carbonate (351mg, 2.54mmol,2.0 equiv.). Then is drawn out and replacedNitrogen was added three times and 1,4-dioxane (4 mL) and water (1 mL) were added under nitrogen blanket. Reacting in an oil bath at 90 ℃ for 24 hours, cooling to room temperature, removing the solvent by reduced pressure distillation, separating the crude product by using a silica gel chromatographic column, and eluting: petroleum ether/ethyl acetate =30, yielding 633mg of white solid, 86% yield. 1 H NMR(500MHz,CDCl 3 )δ1.43(s,9H),1.44(s,9H),3.88(s,3H),7.30–7.35(m,2H),7.36–7.39(m,2H),7.42(dd,J＝7.5,1.0Hz,1H),7.72(d,J＝2.5Hz,1H),7.73–7.76(m,2H),7.79–7.82(m,2H),7.83(d,J＝2.0Hz,1H),7.87(t,J＝7.5Hz,1H),7.90(d,J＝9.0Hz,1H),8.12(t,J＝2.0Hz,1H),8.14–8.17(m,2H),8.87(dd,J＝4.0,2.0Hz,1H)。
Synthesis of ligand L-144 to a Schlenk tube with a magnetic stirrer were added L-144-OMe (603mg, 1.09mmol,1.0 eq.), pyridine hydrochloride (1.26g, 10.9mmol,10.0 eq.). Then the nitrogen was purged three times and 1,3-dimethyl-2-imidazolidinone (4 mL) was added under nitrogen blanket. Reacting in an oil bath at 180 ℃ for 22 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating liquid, drying with anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to remove the solvent. The crude product is separated by a silica gel chromatographic column, and the eluent: petroleum ether/ethyl acetate =50, yielding 478mg of white solid, yield 82%. 1 H NMR(500MHz,CDCl 3 )δ1.48(s,9H),1.49(s,9H),7.26–7.28(m,1H),7.34(ddd,J＝8.0,6.5,1.0Hz,1H),7.40(dd,J＝8.0,4.0Hz,1H),7.44–7.48(m,1H),7.77–7.82(m,4H),7.84(t,J＝1.5Hz,1H),7.87(dd,J＝8.0,1.0Hz,1H),7.90(d,J＝2.0Hz,1H),7.95(t,J＝8.0Hz,1H),8.15(dt,J＝5.5,1.5Hz,2H),8.19(dd,J＝8.0,1.5Hz,1H),8.28(d,J＝8.5Hz,1H),8.91(dd,J＝4.0,2.0Hz,1H),13.04(s,1H)。
Synthesis of Pt-144 to a three-necked flask equipped with a magnetic stirrer were added L-144 (200mg, 0.37mmol,1.0 equiv.), potassium tetrachloroplatinate (162mg, 0.39mmol,1.05 equiv.) and tetrabutylammonium bromide (12mg, 0.037mmol,0.1 equiv.), nitrogen gas was purged three times, acetic acid (25 mL) was added under nitrogen protection, and oxygen was bubbled with nitrogen gas for 30min. Placing the three-mouth bottle into an oil bath kettle with magnetic stirring, stirring at room temperature for 12 hours, heating to 120 ℃ for reaction for 72 hours, cooling to room temperature, and removing by reduced pressure distillationSolvent, the crude product is separated by silica gel chromatographic column, eluent: petroleum ether/dichloromethane =10, 1-1:1, affording 231mg of a reddish-brown solid in 86% yield. 1 H NMR(500MHz,CDCl 3 )δ1.51(s,9H),1.54(s,9H),7.16(ddd,J＝8.0,6.5,1.0Hz,1H),7.30(ddd,J＝8.5,7.0,1.5Hz,1H),7.47(d,J＝9.0Hz,1H),7.62(dd,J＝8.0,5.5Hz,1H),7.71(dd,J＝8.0,1.0Hz,1H),7.72–7.74(m,2H),7.77–7.78(m,2H),7.91(t,J＝7.5Hz,1H),7.94–7.96(m,2H),8.07(d,J＝1.5Hz,1H),8.48(dd,J＝8.0,1.5Hz,1H),8.69(d,J＝2.0Hz,1H),10.75(dd,J＝5.5,1.5Hz,1H)。
Example 15: the synthetic route of the quadridentate ring metal platinum (II) complex phosphorescent luminescent material Pt-142 is as follows:
synthesis of intermediate (L-142-OMe) to a Schlenk tube with a magnetic stirrer were added 8a (593mg, 1.34mmol,1.05 equiv.), 7b (400mg, 1.27mmol,1.0 equiv.), tetrakistriphenylphosphine palladium (45mg, 0.04mmol, 3mol%) and potassium carbonate (351mg, 2.54mmol,2.0 equiv.). The nitrogen was then purged three times and 1,4-dioxane (6 mL) and water (1 mL) were added under nitrogen blanket. Reacting in an oil bath at 85 ℃ for 70 hours, cooling to room temperature, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, and eluting: petroleum ether/ethyl acetate =30, to give 672mg of white solid in 96% yield. 1 H NMR(500MHz,CDCl 3 )δ1.48(s,9H),1.48(s,9H),3.80(s,3H),7.40(dd,J＝8.0,4.0Hz,1H),7.50–7.57(m,2H),7.71(d,J＝8.5Hz,1H),7.75–7.78(m,2H),7.78(t,J＝1.5Hz,1H),7.83–7.88(m,2H),7.89(d,J＝2.5Hz,1H),8.08(dd,J＝7.5,1.0Hz,1H),8.17–8.20(m,2H),8.21(t,J＝1.5Hz,1H),8.23(t,J＝1.5Hz,1H),8.25–8.27(m,1H),8.90(dd,J＝4.0,2.0Hz,1H)。
Synthesis of ligand L-142 to a Schlenk tube with magnetic stirrer was added L-142-OMe (640mg, 1.16mmol,1.0 equiv.), pyridine hydrochloride (1.34g, 11.6mmol,10.0 equiv.). Then the nitrogen was purged three times and 1,3-dimethyl-2-imidazolidinone (3 mL) was added under nitrogen blanket. In 180 ℃ oil bath panAfter reacting for 19 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating liquid, drying with anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate =50, to give 573mg of yellow solid in 90% yield. 1 H NMR(500MHz,CDCl 3 )δ1.52(s,9H),1.54(s,9H),7.37(d,J＝8.5Hz,1H),7.42(dd,J＝8.0,4.0Hz,1H),7.47–7.54(m,2H),7.70(dd,J＝6.0,3.0Hz,1H),7.77(dd,J＝7.0,1.5Hz,1H),7.79(d,J＝2.5Hz,1H),7.89–7.96(m,4H),7.98(d,J＝2.0Hz,1H),8.09(t,J＝1.5Hz,1H),8.17(t,J＝1.5Hz,1H),8.21(dd,J＝8.0,1.5Hz,1H),8.50–8.53(m,1H),8.95(dd,J＝4.0,2.0Hz,1H),16.26(s,1H)。
Synthesis of Pt-142L-142 (300mg, 0.56mmol,1.0 eq), potassium tetrachloroplatinate (244mg, 0.59mmol,1.05 eq) and tetrabutylammonium bromide (18mg, 0.056mmol,0.1 eq) were added to a three-necked flask with a magnetic stirrer, nitrogen was purged three times, acetic acid (25 mL) was added under nitrogen protection, and oxygen was bubbled through with nitrogen for 30min. Putting the three-mouth bottle into an oil bath kettle with magnetic stirring, stirring for 12 hours at room temperature, heating to 120 ℃ for reaction for 55 hours, cooling the reaction to room temperature, then removing the solvent by reduced pressure distillation, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =10, 1-1:1, yielding 180mg of a reddish-brown solid in 44% yield. 1 H NMR(500MHz,CDCl 3 )δ1.52(s,9H),1.55(s,9H),7.12(d,J＝9.0Hz,1H),7.50–7.57(m,2H),7.72–7.75(m,3H),7.78(d,J＝1.5Hz,1H),7.80(d,J＝2.0Hz,1H),7.89(d,J＝9.0Hz,1H),7.98–8.05(m,2H),8.10(d,J＝1.0Hz,1H),8.51(dd,J＝8.0,1.5Hz,1H),8.70(d,J＝2.0Hz,1H),8.83(dd,J＝7.5,1.0Hz,1H),10.98(dd,J＝5.5,1.5Hz,1H)。
Example 16: the synthetic route of the tetradentate ring metal platinum (II) complex phosphorescent luminescent material Pt-591 is as follows:
synthesis of intermediate (L-591-OMe) 9a (500mg, 1.08mm) was added to a Schlenk tube with a magnetic stirrerol,1.0 equiv.), 2b (430mg, 1.29mmol,1.2 equiv.), tetrakistriphenylphosphine palladium (37mg, 0.032mmol,3 mol%) and potassium carbonate (298mg, 2.16mmol,2.0 equiv.). The nitrogen was then purged three times and 1,4-dioxane (5 mL) and water (1 mL) were added under nitrogen blanket. Reacting in an oil bath at 100 ℃ for 20 hours, cooling to room temperature, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, and eluting: petroleum ether/ethyl acetate =30, yielding 505mg of white solid in 74% yield. 1 H NMR(500MHz,CDCl 3 )δ1.33(s,9H),1.45(s,9H),1.48(s,9H),3.43(s,3H),7.38–7.46(m,3H),7.49–7.53(m,2H),7.74–7.80(m,6H),7.83(t,J＝1.5Hz,1H),8.02(d,J＝2.0Hz,1H),8.09(d,J＝2.0Hz,1H),8.27(dd,J＝8.0,2.0Hz,1H),8.29(t,J＝1.5Hz,1H),8.30(t,J＝1.5Hz,1H),8.96(dd,J＝4.0,2.0Hz,1H)。
Synthesis of ligand L-591 to a Schlenk tube with a magnetic stirrer were added L-591-OMe (468mg, 0.74mmol,1.0 equiv.), pyridine hydrochloride (855mg, 7.4mmol,10.0 equiv.). Then the nitrogen was purged three times and 1,3-dimethyl-2-imidazolidinone (3 mL) was added under nitrogen blanket. Reacting in an oil bath at 180 ℃ for 12 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating liquid, drying with anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to remove the solvent. Separating the obtained crude product by using a silica gel chromatographic column, and eluting the mixture by using an eluent: petroleum ether/ethyl acetate =50, 1-10, yielding 392mg of a white solid in 86% yield. 1 H NMR(500MHz,CDCl 3 )δ1.37(s,9H),1.49(s,18H),7.41–7.45(m,2H),7.46(dd,J＝8.0,4.0Hz,1H),7.51–7.54(m,2H),7.69(dd,J＝6.0,2.5Hz,1H),7.72(d,J＝2.5Hz,1H),7.78–7.81(m,2H),7.86–7.90(m,3H),8.05(d,J＝2.0Hz,1H),8.10(d,J＝2.0Hz,1H),8.15(dt,J＝6.5,1.5Hz,2H),8.28(dd,J＝8.5,1.5Hz,1H),9.01(dd,J＝4.0,2.0Hz,1H),15.08(s,1H)。
Synthesis of Pt-591 into a three-necked flask with a magnetic stirrer, L-591 (250mg, 0.40mmol,1.0 equiv.), potassium tetrachloroplatinate (176mg, 0.42mmol,1.05 equiv.) and tetrabutylammonium bromide (14mg, 0.04mmol,0.1 equiv.) were added, nitrogen was purged three times, acetic acid (24 mL) was added under nitrogen protection, and oxygen was bubbled with nitrogen for 30min. Putting the three-mouth bottle into an oil bath pan with magnetic stirringStirring at room temperature for 12 hours, heating to 120 ℃ for reaction for 74 hours, cooling the reaction to room temperature, then distilling under reduced pressure to remove the solvent, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =10, 1-1:1, yielding 250mg of a tan solid in 77% yield. 1 H NMR(500MHz,CDCl 3 )δ1.37(s,9H),1.48(s,9H),1.63(s,9H),7.47–7.51(m,1H),7.51(d,J＝2.5Hz,1H),7.56–7.62(m,4H),7.74(d,J＝7.5Hz,1H),7.75(d,J＝1.5Hz,1H),7.80–7.83(m,2H),7.92(d,J＝7.5Hz,1H),7.98(t,J＝8.0Hz,1H),8.02(d,J＝2.0Hz,1H),8.07(d,J＝1.0Hz,1H),8.55(dd,J＝8.0,1.5Hz,1H),8.74(d,J＝2.0Hz,1H),10.86(dd,J＝5.5,1.5Hz,1H)。
Example 17: the synthetic route of the tetradentate ring metal platinum (II) complex phosphorescent luminescent material Pt-592 is as follows:
synthesis of intermediate (L-592-OMe) into a Schlenk tube with a magnetic stirrer were added 10a (407mg, 1.0mmol,1.0 equiv.), 2b (332mg, 1.0mmol,1.0 equiv.), tetrakistriphenylphosphine palladium (35mg, 0.03mmol, 3mol%) and potassium carbonate (276mg, 2.0mmol,2.0 equiv.). The nitrogen was then purged three times and 1,4-dioxane (4 mL) and water (1 mL) were added under nitrogen blanket. Reacting in an oil bath kettle at 100 ℃ for 20 hours, cooling to room temperature, distilling under reduced pressure to remove the solvent, separating the crude product by using a silica gel chromatographic column, eluting: petroleum ether/ethyl acetate =30, yielding 443mg of white solid in 77% yield. 1 H NMR(500MHz,CDCl 3 )δ1.30(s,9H),1.44(s,9H),3.40(s,3H),7.37(d,J＝2.5Hz,1H),7.39–7.43(m,1H),7.45(dd,J＝8.0,4.0Hz,1H),7.48–7.52(m,2H),7.63–7.66(m,2H),7.74–7.78(m,5H),7.84(ddd,J＝7.5,2.0,1.5Hz,1H),8.03(d,J＝2.5Hz,1H),8.10(d,J＝2.0Hz,1H),8.21(ddd,J＝8.0,2.0,1.0Hz,1H),8.28(dd,J＝8.5,2.0Hz,1H),8.50(t,J＝3.5Hz,1H),8.96(dd,J＝4.0,2.0Hz,1H)。
Synthesis of ligand L-592 to a Schlenk tube with a magnetic stirrer were added L-592-OMe (415mg, 0.72mmol,1.0 equiv.), pyridine hydrochloride (831mg, 7.2mmol,10.0 equiv.). Then is taken outNitrogen was changed three times and 1,3-dimethyl-2-imidazolidinone (3 mL) was added under nitrogen blanket. Reacting in an oil bath kettle at 180 ℃ for 15 hours, cooling to room temperature, adding ethyl acetate for dilution, washing an organic phase with water, separating liquid, drying with anhydrous sodium sulfate, filtering, and distilling the filtrate under reduced pressure to remove the solvent. The crude product is separated by a silica gel chromatographic column, and the eluent: petroleum ether/ethyl acetate =50, 1-10, yielding 360mg of white solid in 89% yield. 1 H NMR(500MHz,CDCl 3 )δ1.37(s,9H),1.48(s,9H),7.40(d,J＝2.5Hz,1H),7.43(dt,J＝7.0,1.5Hz,1H),7.47(dd,J＝8.0,4.0Hz,1H),7.50–7.54(m,2H),7.68–7.71(m,3H),7.78–7.81(m,2H),7.88–7.90(m,3H),8.02–8.04(m,1H),8.05(d,J＝2.0Hz,1H),8.12(d,J＝2.5Hz,1H),8.29(dd,J＝8.5,2.0Hz,1H),8.35(t,J＝7.5Hz,1H),9.01(dd,J＝4.0,1.5Hz,1H),14.82(s,1H)。
Synthesis of Pt-592 into a three-necked flask with a magnetic stirrer, L-592 (200mg, 0.36mmol,1.0 eq), potassium tetrachloroplatinate (154mg, 0.37mmol,1.05 eq) and tetrabutylammonium bromide (12mg, 0.036mmol,0.1 eq) were added, nitrogen was purged three times, acetic acid (23 mL) was added under nitrogen protection, and oxygen was bubbled with nitrogen for 30min. Putting the three-mouth bottle into an oil bath kettle with magnetic stirring, stirring for 12 hours at room temperature, heating to 120 ℃ for reaction for 73 hours, cooling the reaction to room temperature, then removing the solvent by reduced pressure distillation, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =10, 1-1:1, yielding 250mg of a tan solid in 92% yield. 1 H NMR(500MHz,CDCl 3 )δ1.37(s,9H),1.62(s,9H),7.36(t,J＝7.5Hz,1H),7.46–7.52(m,2H),7.55–7.59(m,3H),7.62(dd,J＝8.0,5.5Hz,1H),7.69(dt,J＝7.5,1.0Hz,2H),7.80–7.82(m,2H),7.92–7.99(m,2H),8.03–8.05(m,2H),8.56(dd,J＝8.0,1.5Hz,1H),8.77(d,J＝2.0Hz,1H),10.88(dd,J＝5.5,1.5Hz,1H)。
Example 18: the synthetic route of the quadridentate ring metal palladium (II) complex phosphorescent luminescent material Pd-183 is as follows:
synthesis of Pd-183 into the magnetic bandA three-necked flask with a force stirrer was charged with L-183 (200mg, 0.31mmol,1.0 equiv.), palladium acetate (72mg, 0.22mmol,1.05 equiv.), and tetrabutylammonium bromide (10mg, 0.03mmol,0.1 equiv.), nitrogen was purged three times, acetic acid (20 mL) was added under nitrogen protection, and nitrogen was bubbled to remove oxygen for 30min. Putting the three-mouth bottle into an oil bath kettle with magnetic stirring, heating to 100 ℃ for reaction for 75 hours, cooling the reaction to room temperature, then carrying out reduced pressure distillation to remove the solvent, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =5:1-1:1 to give 150mg of yellow solid in 64% yield. 1 H NMR(500MHz,CDCl 3 )δ1.37(s,9H),1.60(s,9H),7.32(ddd,J＝8.0,7.0,1.0Hz,2H),7.42–7.50(m,6H),7.60(dd,J＝6.5,2.5Hz,1H),7.68–7.72(m,2H),7.81(d,J＝2.0Hz,1H),7.86–7.91(m,2H),7.93(dd,J＝8.0,1.0Hz,1H),8.05(d,J＝1.5Hz,1H),8.20(t,J＝1.0Hz,1H),8.21(t,J＝1.0Hz,1H),8.43(dd,J＝8.0,1.5Hz,1H),8.52(dd,J＝8.0,1.5Hz,1H),10.65(dd,J＝5.0,1.5Hz,1H)。
Example 19: the synthetic route of the quadridentate ring metal palladium (II) complex phosphorescent luminescent material Pd-124 is as follows:
synthesis of Pd-124, L-124 (270mg, 0.50mmol,1.0 equiv.), palladium acetate (117mg, 0.52mmol,1.05 equiv.) and tetrabutylammonium bromide (1695g, 0.05mmol,0.1 equiv.) were added to a three-necked flask with a magnetic stirrer, nitrogen was purged three times, acetic acid (30 mL) was added under nitrogen protection, and nitrogen was bubbled for 30min to remove oxygen. Putting the three-mouth bottle into an oil bath kettle with magnetic stirring, heating to 120 ℃ for reaction for 90 hours, cooling the reaction to room temperature, then carrying out reduced pressure distillation to remove the solvent, separating the obtained crude product by using a silica gel chromatographic column, and eluting the solvent: petroleum ether/dichloromethane =5:1-1:1 to give 121mg of yellow solid in 37% yield. 1 H NMR(500MHz,CDCl 3 )δ1.35(s,9H),1.52(s,9H),1.56(s,9H),7.35(t,J＝7.5Hz,1H),7.42–7.45(m,2H),7.60(dd,J＝8.0,5.0Hz,1H),7.63–7.66(m,2H),7.80–7.82(m,2H),7.88(q,J＝7.5Hz,2H),8.43(dd,J＝8.0,1.5Hz,1H),8.57(d,J＝2.0Hz,1H),10.48(dd,J＝5.0,1.5Hz,1H)。
Example 20: the synthetic route of the quadridentate ring metal palladium (II) complex phosphorescent luminescent material Pd-210 is as follows:
synthesis of Pd-210 into a three-necked flask with magnetic stirrer were added L-210 (150mg, 0.27mmol,1.0 equiv.), palladium acetate (63mg, 0.28mmol,1.05 equiv.) and tetrabutylammonium bromide (9mg, 0.027mmol,0.1 equiv.), nitrogen was purged three times, acetic acid (15 mL) was added under nitrogen protection, and nitrogen was bubbled for 30min to remove oxygen. Putting the three-mouth bottle into an oil bath kettle with magnetic stirring, heating to 120 ℃ for reaction for 48 hours, cooling the reaction to room temperature, then carrying out reduced pressure distillation to remove the solvent, separating the obtained crude product by using a silica gel chromatographic column, and eluting: petroleum ether/dichloromethane =1:1 to give 80mg of yellow solid in 44% yield. 1 H NMR(500MHz,CDCl 3 )δ1.38(s,9H),1.40(s,9H),6.67(dd,J＝8.0,5.0Hz,1H),7.15(d,J＝2.0Hz,1H),7.23–7.25(m,2H),7.43(t,J＝7.5Hz,2H),7.51–7.57(m,3H),7.69(d,J＝7.5Hz,1H),7.78–7.80(m,2H),7.91(d,J＝2.5Hz,1H),8.00(t,J＝7.0Hz,1H),8.06(d,J＝2.0Hz,1H),8.11(d,J＝8.0Hz,1H),8.16(d,J＝2.5Hz,1H),9.95–9.96(m,1H)。
Experimental data and analysis:
divalent platinum metal complexes based on bidentate ligands generally have low phosphorescent quantum efficiencies, generally less than 30%, (organic Chemistry 2002,41,3055-3066.); the half-width of the emission spectrum in dichloromethane solution at room temperature was about 100nm and the quantum efficiency in polymethyl methacrylate (PMMA) was 40% for a classical red-light tetradentate ring metal platinum complex PtON11Me (Organic Electronics 2014,15,1862-1867.).
Table 1 and fig. 1 to 5 show the results of photophysical property tests of the divalent platinum and palladium metal complex (phosphorescent material) of the present invention in a dichloromethane solution at room temperature, and the data in the table show that the emission wavelength of the divalent platinum metal complex phosphorescent material is between 611 and 626nm, which is a red light emitting region; the half-peak width is small and is below 60nm, and the color purity is high; the quantum efficiency of the material in polymethyl methacrylate (PMMA) is higher, more than 50 percent, even more than 80 percent; the thermal decomposition temperature is higher than 300 ℃, even more than 350 ℃, and the preparation of the thermal evaporation OLED device can be satisfied. Meanwhile, the photophysical properties can be efficiently regulated and controlled by regulating and controlling the central metal ions, for example, the Pd-124 can realize the white light luminescence of single molecules.
TABLE 1 photophysical property test results of divalent platinum and palladium metal complexes of the invention in dichloromethane solution at room temperature
Note: the molecular structure is as follows:
therefore, the bivalent platinum metal complex molecule has certain application value in the fields of OLED display, illumination and the like.
Meanwhile, we have carried out DFT theoretical calculation on part of the platinum complexes, as shown in table 2 below, the energy levels of the lowest unoccupied orbital (LUMO) and the highest occupied orbital (HOMO) of the material molecule can be regulated by regulating the ligand structure and type to meet the matching with different device structures; meanwhile, it can be seen from Table 2 that the band gap between HOMO and LUMO is 2.30-2.70eV.
Table 2. Front orbital energy level and band gap of the obtained complex by theoretical calculation
Note: the molecular structure is as follows:
device embodiments
Each layer of the organic light emitting device of the present invention can be formed by a method such as vacuum evaporation, sputtering, ion plating, or the like, or a wet film formation method such as spin coating, printing, or the like, and the solvent used is not particularly limited.
In a preferred embodiment of the present invention, the OLED device according to the invention comprises a hole transport layer, which may preferably be selected from known or unknown materials, particularly preferably from the following structures, without representing the present invention being limited to the following structures:
in a preferred embodiment of the present invention, the hole transport layer contained in the OLED device of the present invention comprises one or more p-type dopants. Preferred p-type dopants of the present invention are, but do not represent a limitation of the present invention to:
in a preferred embodiment of the present invention, the electron transport layer may be selected from at least one of the compounds ET-1 to ET-13, but does not represent that the present invention is limited to the following structures:
the electron transport layer may be formed from an organic material in combination with one or more n-type dopants (e.g., liQ).
OLED device examples:
specifically, the structure of the bottom-emitting OLED device is that a Hole Injection Layer (HIL) is HT-1:P-3 (95: 5v/v%), and the thickness is 10 nanometers; the Hole Transport Layer (HTL) is HT-1 and has a thickness of 90 nm; the Electron Blocking Layer (EBL) is HT-10 and has a thickness of 10 nanometers, the luminescent layer (EML) is a main body material (RH), the platinum metal complex (95: liQ (50. The host material (RH) can be selected from the following structures:
the organic light emitting device was fabricated at 10mA/cm using standard methods known in the art 2 Voltage, efficiency and life were tested under current conditions.
Table 3. Results of performance test of the organic light emitting devices prepared in the examples of the present invention and the comparative examples.
As shown in table 3, the device structures in the above examples and comparative examples are consistent except for the difference in the light emitting layer, and the device performance based on PtON11Me is taken as a reference, and the device including the divalent platinum metal complex of the present invention has significantly improved current efficiency and improved lifetime compared to the conventional organic light emitting device. In conclusion, the novel divalent platinum metal complex has a great application value in organic photoelectric devices.
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.
Claims (7)
1. A divalent platinum or palladium metal complex phosphorescent material based on 8-phenylquinoline and derivative coordination thereof is characterized by having a structure shown in a general formula (I):
wherein:
m is Pt or Pd;
x is O, S or NR;
Y 1 、Y 2 、Y 3 、Y 4 、Y 5 、Y 6 、Y 7 、Y 8 、Y 9 、Y 10 、Y 11 、Y 12 、Y 13 、Y 14 、Y 15 and Y 16 Each independently selected from an N or C atom;
R、R 1 、R 2 、R 3 、R 4 and R 5 Each independently may be mono-, di-, tri-, tetra-, or unsubstituted; r 1 、R 2 、R 3 、R 4 And R 5 Each independently represents hydrogen, deuterium, C1-C24 alkyl, C1-C24 haloalkyl, C1-C24 cycloalkyl, C1-C24 alkoxy, C1-C24 aryl, C1-C24 heteroaryl, C1-C24 aryloxy, halogen, cycloalkenyl, heterocyclyl, alkenyl, alkynyl, hydroxyl, mercapto, nitro, cyano, amino, mono-or di-C1-C24 alkylamino, mono-or di-C1-C24 arylamino, ester, nitrile, isonitrile, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, silyl or substituted silyl or a polymeric silylAnd two or more adjacent R, R 1 、R 2 、R 3 、R 4 And R 5 The rings may be selectively linked to form a ring.
2. The 8-phenylquinoline and derivative thereof coordinated divalent platinum or palladium metal complex phosphorescent material as claimed in claim 1, wherein the divalent platinum metal complex luminescent material has a structure of one of the following:
3. an organic light-emitting device comprising a cathode, an anode, and an organic layer including at least a light-emitting layer; the organic layer comprises the divalent platinum or palladium metal complex phosphorescent material based on 8-phenylquinoline and derivative coordination thereof in claim 1 or 2.
4. The organic light-emitting device of claim 3, wherein the organic layer further comprises one or more of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer.
5. The organic light-emitting device according to claim 3, wherein the light-emitting layer further comprises a host material, wherein the volume ratio of the host material to the divalent platinum or palladium metal complex phosphorescent material is 1:99 to 99: 1.
6. The organic light-emitting device according to claim 3, wherein the organic light-emitting device is a full-color display, a photovoltaic device, a light-emitting display device, or an organic light-emitting diode.
7. A display or illumination apparatus comprising the organic light-emitting device according to any one of claims 3 to 6.
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