CN113527372A - Divalent platinum metal complex, organic light-emitting device, and display or lighting device - Google Patents

Divalent platinum metal complex, organic light-emitting device, and display or lighting device Download PDF

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CN113527372A
CN113527372A CN202111077133.5A CN202111077133A CN113527372A CN 113527372 A CN113527372 A CN 113527372A CN 202111077133 A CN202111077133 A CN 202111077133A CN 113527372 A CN113527372 A CN 113527372A
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metal complex
platinum metal
organic light
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CN113527372B (en
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李贵杰
佘远斌
郭华
刘顺
湛丰
赵晓宇
王子兴
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Zhejiang University of Technology ZJUT
Zhejiang Huadisplay Optoelectronics Co Ltd
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Zhejiang Huadisplay Optoelectronics Co Ltd
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    • 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
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Abstract

The present invention provides a divalent platinum metal complex, an organic light-emitting device, and a display or lighting apparatus, wherein the divalent platinum metal complex has a structure represented by general formula (I):
Figure 100004_DEST_PATH_IMAGE001
(I) compared with a bidentate ligand bivalent platinum complex, the bivalent platinum metal complex based on the tetradentate ligand has strong molecular rigidity, can effectively inhibit non-radiative transition generated by molecular vibration, is beneficial to maintaining high quantum efficiency, and greatly improves sublimation performance. Devices comprising the divalent platinum metal complexes of the invention, in contrast to conventional organic hairThe current efficiency of the optical device is obviously improved, and the service life of the optical device is also prolonged.

Description

Divalent platinum metal complex, organic light-emitting device, and display or lighting device
Technical Field
The invention relates to a divalent platinum metal complex, in particular to a divalent platinum metal complex, an organic light-emitting device and a display or lighting device, and belongs to the field of metal organic photoelectric materials.
Background
Compared with Liquid Crystal Displays (LCDs), organic light emitting devices, such as organic light emitting diode devices (OLEDs), have many advantages, such as lightness and thinness, gorgeous color, high color saturation, energy saving, wide viewing angle, fast response speed, and the like. Therefore, the potential application of the organic light emitting device in the fields of display and illumination is attracting attention. However, the design and development of light emitting materials is central to the OLED field. In early OLED devices, the light-emitting material was mainly organic small molecule fluorescent material. Spin statistical quantum, however, indicates that in the case of electroluminescence, the ratio of singlet excitons to triplet excitons (exiton) is 1:3, and the conventional fluorescent material can only utilize excitons in the singlet excited state, and thus, the theoretical internal quantum efficiency thereof is only 25%. The Forrest professor at Prolington university, USA, and Thompson at southern California university, teach 1998 to find the phenomenon of phosphorescence electroluminescence of heavy metal organic complex molecules at room temperature. Due to the strong spin-orbit coupling of heavy metal atoms, the complex can effectively promote the intersystem crossing (ISC) of excitons from singlet state to triplet state, so that the OLED device can fully utilize electric excitation to generate all singlet state and triplet state excitons, and the theoretical internal quantum efficiency of the luminescent material can reach 100% ((See also,M. A. Baldo, D. F. O’Brien et al., highly efficient phosphorescent emission from organic electroluminescent devices, Nature, 1998, 395, 151-154.）。
At present, the heavy metal phosphorescent organic complex molecules which can meet the practical application are basically ringsA metal trivalent iridium (III)) complex molecule, 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 material3 .H2The price of O is much higher than that of PtCl for preparing bivalent platinum (II)) complex phosphorescent material2. In addition, the preparation of the trivalent iridium complex phosphorescent material involves ligand exchange of a trivalent iridium-containing dimer and a trivalent iridium intermediate,merSynthesis of iridium (III) complexes andmer-tofacThe isomer of the iridium (III) complex is converted into four steps of reaction, so that the total yield is greatly reduced, and the raw material IrCl is greatly reduced3 .H2The 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.
Although highly efficient divalent platinum complex phosphorescent materials have been reportedSee also，Guijie Li, A. Wolfe et al., modifying emission spectral bandwidth of phosphorescent platinum(II) complexes through synthetic control, Inorganic Chemistry, 2017, 56, 8244–8256.; Guijie Li, Xiangdong Zhao., Tetradentate Platinum(II) Complexes for Highly Efficient Phosphorescent Emitters and Sky Blue OLEDs, Chemistry of Materials2020, 32, 537 and 548.), but divalent platinum complex phosphorescent materials which can meet the practical use requirements are still not reported. However, the main problems of the divalent platinum complex phosphorescent materials are insufficient thermal stability, difficult molecular purification and the like. Since divalent platinum is dsp2Hybridization is carried out, the molecules with plane configuration are easy to interact with each other to cause the accumulation of the molecules, thereby leading the red shift of the luminous color of the OLED, simultaneously leading the OLED to be difficult to diffuse under the vacuum condition, easy to decompose and difficult to sublimate and purify, and greatly reducing the service life of OLED devices due to low purity. In addition, the emission color is adjusted to a standard three primary color region, such as between 510 ‒ 530nm for green light, etc.
Therefore, there is a need to develop a novel divalent platinum metal complex based on a trimethylphenylpyridine structural unit.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a bivalent platinum metal complex (green phosphorescent material) based on a trimethylphenyl pyridine structural unit 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 divalent platinum metal complex, which has a structure shown in a general formula (I):
Figure 512066DEST_PATH_IMAGE001
（I）
wherein the content of the first and second substances,
Ra、Rband RcEach independently represents methyl, mono-deuterated methyl, di-deuterated methyl or per-deuterated methyl;
R1、R2、R3、R4and R5Each independently may be mono-, di-, tri-, tetra-, or unsubstituted; r1、R2、R3、R4And R5Each independently represents hydrogen, deuterium, alkyl of C1 ‒ C24, haloalkyl of C1 ‒ C24, cycloalkyl of C1 ‒ C24, alkoxy of C1 ‒ C24, aryl of C1 ‒ C24, heteroaryl of C1 ‒ C24, aryloxy of C1 ‒ C24, halogen, cycloalkenyl, heterocyclyl, alkenyl, alkynyl, hydroxyl, mercapto, nitro, cyano, amino, alkylamino of mono or di C1 ‒ C24, arylamino of mono or di C1 ‒ C24, ester group, nitrile group, isonitrile group, alkoxycarbonyl, amido group, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazino, silylA substituted silyl group, or a polymeric group, and two or more adjacent R1、R2、R3、R4And R5The rings may be selectively linked to form a ring.
Further, the divalent platinum metal complex has a structure of one of the following, but is not limited thereto:
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。
the invention also provides an organic light-emitting device which comprises a cathode, an anode and an organic layer, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer and an electron injection layer, and the organic layer comprises the divalent platinum metal complex.
Further, the organic functional layer is a light emitting layer, and the light emitting layer further comprises a host material, wherein the volume ratio of the host material to the divalent platinum metal complex 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 bivalent platinum metal complex molecule based on the bidentate ligand has lower rigidity, the two bidentate ligands are easy to twist and vibrate to cause non-radiative decay, so that the phosphorescence quantum efficiency is low, and the ring bivalent platinum metal complex molecule based on the tridentate ligand needs a second complex anion (such as alkyne anion and Cl)‒Carbenes, etc.), which also results in reduced chemical and thermal stability of the complex. The above reasons are not favorable for its application as a phosphorescent material in OLED devices. The invention has the beneficial effects that: firstly, the quadridentate ligand adopted in the method can improve the molecular rigidity of the divalent platinum metal complex, and can effectively inhibitNon-radiative transition generated due to molecular vibration is produced, and high quantum efficiency is kept; secondly, a trimethylphenyl group is introduced into the 4 th site of a pyridine ring in a molecule, and due to the steric effect of methyl groups on two ortho-positions of the phenyl group, a benzene ring and the pyridine ring tend to be vertical, the rotation of the benzene ring and the non-radiative transition generated by the rotation of the benzene ring can be inhibited, and the high quantum efficiency is favorably kept; in addition, the conjugation between the benzene ring and the pyridine ring can be eliminated, and the generated luminescence red shift is avoided; thirdly, the introduction of the high steric hindrance trimethylphenyl can also inhibit the mutual action among the bivalent platinum metal complex molecules to cause the accumulation of the molecules, which is beneficial to the diffusion of the molecules under the vacuum condition and the sublimation purification. 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 a compound LC11 of the present invention in a dichloromethane solution at room temperature.
FIG. 2 is a photoluminescence spectrum of a compound LC12 of the present invention in a dichloromethane solution at room temperature.
FIG. 3 is a photoluminescence spectrum of a compound LC18 of the present invention in a dichloromethane solution at room temperature.
FIG. 4 is a photoluminescence spectrum of a compound LC19 of the present invention in a dichloromethane solution at room temperature.
FIG. 5 is a photoluminescence spectrum of compound PtON1Ph in dichloromethane 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 (I) 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.
The invention discloses application of a divalent platinum metal complex luminescent material containing a quinoline structure unit in 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 (I) can be applied to organic light emitting devices such as organic photoluminescent devices or organic electroluminescent devices as a light emitting material. 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 used3As a solvent, thenHydrogen spectrum by CDCl3(δ =7.26 ppm) as an internal standard. If DMSO-d is used6As a solvent, the hydrogen spectrum is DMSO-d 6 (δ = 2.50 ppm) as an internal standard. The following abbreviations (or combinations) are used to interpret the hydrogen peaks: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad.
Example 1: LC11 can be prepared as follows:
Figure 343311DEST_PATH_IMAGE188
Figure 589616DEST_PATH_IMAGE189
。
(1) synthesis of ligand LC 11-L: to a dry sealed tube with a magnetic rotor were added 1-Br (2.43 g, 8.37 mmol, 1.1 equiv.), 1-OH (2.88 g, 7.61 mmol, 1.0 equiv.), cuprous iodide (579 mg, 3.04 mmol, 40 mol%), 2-picolinic acid (750 mg, 6.09 mmol, 80 mol%) and potassium phosphate (3.23 g, 15.22 mmol, 2.0 equiv.) in that order, nitrogen was purged three times, and dimethyl sulfoxide (40 mL) was added under nitrogen protection. Placing the sealed tube in an oil bath kettle at 110 ℃ for stirring, reacting for 2.5 days, cooling to room temperature, washing with water, adding ethyl acetate for extraction, extracting a water layer with ethyl acetate for three times, combining organic phases, washing the organic phases with brine once, drying with anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum ether/ethyl acetate = 20: 1-10: 1, yielding product LC11-L, 3.01 g as a foamy solid, yield 67%.1H NMR (500 MHz, CDCl3): δ 1.36 (s, 9H), 2.02 (s, 6H), 2.31 (s, 3H), 6.91 (s, 2H), 7.06−7.08 (m, 2H), 7.23−7.25 (m, 2H), 7.30−7.33 (m, 1H), 7.39−7.42 (m, 3H), 7.59 (d, J = 2.0 Hz, 1H), 7.64 (d, J = 8.0 Hz, 1H), 7.72−7.76 (m, 1H), 7.84−7.86 (m, 2H), 8.05−8.07 (m, 2H), 8.68 (d, J= 4.0 Hz, 1H), 8.70 (dd, J = 4.5, 0.5 Hz, 1H)。
(2) Synthesis of LC 11: to the magnetic forceA500 mL dry three-necked flask with condenser was charged with LC11-L (3.00 g, 5.10 mmol, 1.0 equiv.), potassium chloroplatinite (2.22 g, 5.36 mmol, 1.05 equiv.), tetra-n-butylammonium bromide (164 mg, 0.51 mmol, 0.1 equiv.), purged with nitrogen three times, and charged with acetic acid (290 mL) with nitrogen purged beforehand. After bubbling reaction liquid nitrogen for 30 minutes, the reaction was stirred at room temperature for 12 hours, then stirred at 120 ℃ for 2 days, cooled to room temperature, the solvent was distilled off under reduced pressure, stannous chloride (1.93 g, 10.20 mmol, 2.0 equiv.) and methylene chloride (200 mL) were added, and the mixture was stirred at room temperature for 1 day. The reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined and the solvent was distilled off under reduced pressure. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum ether/dichloromethane = 3: 1-1: 1 to give product LC11 as a pale yellow solid, 2.96 g, yield 74%.1H NMR (400 MHz, CDCl3): δ 1.44 (s, 9H), 2.11 (s, 6H), 2.34 (s, 3H), 6.96 (dd, J = 6.0, 1.6 Hz, 1H), 6.98 (s, 2H), 7.28−7.40 (m, 5H), 7.60 (d, J = 1.6 Hz, 1H), 7.78−7.81 (m, 2H), 7.92−8.04 (m, 4H), 8.81 (d, J = 5.2 Hz, 1H), 9.09 (d, J = 6.0 Hz, 1H)。
Example 2: LC12 can be prepared as follows:
Figure 352167DEST_PATH_IMAGE190
Figure 51132DEST_PATH_IMAGE191
。
(1) synthesis of ligand LC 12-L: to a dry sealed tube with a magnetic rotor were added 2-Br (2.39 g, 7.84 mmol, 1.1 equiv.), 1-OH (2.70 g, 7.13 mmol, 1.0 equiv.), cuprous iodide (543 mg, 2.85 mmol, 40 mol%), 2-picolinic acid (702 mg, 5.70 mmol, 80 mol%) and potassium phosphate (3.03 g, 14.26 mmol, 2.0 equiv.) in that order, nitrogen was purged three times, and dimethyl sulfoxide (40 mL) was added under nitrogen protection. Placing the sealed tube in an oil bath kettle at 110 deg.C, stirring, reacting for 3 days, cooling to room temperature, washing with water, and extracting with ethyl acetateThe aqueous layer was extracted three times with ethyl acetate, the organic phases were combined, washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum ether/ethyl acetate = 20: 1-10: 1, yielding product LC12-L, 3.12 g as a foamy solid, yield 73%.1H NMR (400 MHz, CDCl3): δ 1.35 (s, 9H), 2.01 (s, 6H), 2.31 (s, 3H), 2.36 (s, 3H), 6.91 (s, 2H), 7.02 (d, J = 5.2 Hz, 1H), 7.05−7.08 (m, 2H), 7.21 (t, J = 2.0 Hz, 1H), 7.32 (t, J = 7.2 Hz, 1H), 7.39−7.43 (m, 4H), 7.58 (d, J = 2.4 Hz, 1H), 7.80 (t, J = 2.0 Hz, 1H), 7.86 (d, J = 8.4 Hz, 1H), 8.04−8.07 (m, 2H), 8.50 (d, J = 5.2 Hz, 1H)。
(2) Synthesis of LC 12: to a 500 mL dry three-necked flask equipped with a magnetic rotor and a condenser were added LC12-L (2.9 g, 4.82 mmol, 1.0 equiv.), potassium chloroplatinite (2.10 g, 5.06 mmol, 1.05 equiv.), tetra-n-butylammonium bromide (155 mg, 0.48 mmol, 0.1 equiv.), nitrogen gas was purged three times, and acetic acid (290 mL) previously bubbled with nitrogen gas. After bubbling reaction liquid nitrogen for 30 minutes, the reaction was stirred at room temperature for 12 hours, then stirred at 120 ℃ for 2 days, cooled to room temperature, the solvent was distilled off under reduced pressure, stannous chloride (1.83 g, 9.64 mmol, 2.0 equiv.) and methylene chloride (200 mL) were added, and the mixture was stirred at room temperature for 1 day. The reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined and the solvent was distilled off under reduced pressure. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum ether/dichloromethane = 3: 1-1: 1 to give product LC12 as a light yellow solid 2.67 g, yield 70%.1H NMR (400 MHz, DMSO-d 6 ): δ 1.41 (s, 9H), 2.10 (s, 6H), 2.29 (s, 3H), 2.54 (s, 3H), 7.01 (s, 2H), 7.13 (d, J = 1.6 Hz, 1H), 7.21−7.26 (m, 2H), 7.36 (d, J = 7.6 Hz, 1H), 7.41−7.48 (m, 2H), 7.77 (d, J = 1.6 Hz, 1H), 7.83 (d, J = 1.6 Hz, 1H) 7.86 (d, J = 8.4 Hz, 1H), 7.91 (d, J = 8.0 Hz, 1H), 8.13 (dd, J = 7.2, 1.2 Hz, 1H), 8.25 (s, 1H), 8.71 (d, J = 5.6 Hz, 1H), 9.09 (d, J = 6.0 Hz, 1H)。
Example 3: LC18 can be prepared as follows:
Figure 173809DEST_PATH_IMAGE192
Figure 212303DEST_PATH_IMAGE193
。
(1) synthesis of ligand LC 18-L: to a dry sealed tube with a magnetic rotor were added 2-Br (538 mg, 1.77 mmol, 1.1 equiv.), 2-OH (700 mg, 1.61 mmol, 1.0 equiv.), cuprous iodide (122 mg, 0.64 mmol, 40 mol%), 2-picolinic acid (159 mg, 1.29 mmol, 80 mol%) and potassium phosphate (684 g, 3.22 mmol, 2.0 equiv.) in that order, nitrogen was purged three times, and dimethyl sulfoxide (10 mL) was added under nitrogen protection. Placing the sealed tube in an oil bath kettle at 110 ℃ for stirring, reacting for 2 days, cooling to room temperature, washing with water, adding ethyl acetate for extraction, extracting a water layer with ethyl acetate for three times, combining organic phases, washing the organic phases with brine once, drying with anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum ether/ethyl acetate = 20: 1-10: 1, yielding product LC18-L, 872 mg as a foamy solid in 82% yield.1H NMR (500 MHz, CDCl3): δ 1.37 (s, 9H), 1.46 (s, 9H), 2.03 (s, 6H), 2.32 (s, 3H), 2.37 (s, 3H), 6.92 (s, 2H), 7.04−7.09 (m, 3H), 7.22 (t, J = 2.0 Hz, 1H), 7.41−7.43 (m, 3H), 7.50 (dd, J = 9.0, 2.0 Hz, 1H), 7.63 (d, J = 2.0 Hz, 1H), 7.81−7.83 (m, 2H), 8.07−8.09 (m, 2H), 8.52 (d, J = 5.0 Hz, 1H), 8.70 (d, J = 5.0, 0.5 Hz, 1H)。
(2) Synthesis of LC 18: to a 250 mL dry three-necked flask equipped with a magnetic rotor and condenser were added LC18-L (850 mg, 1.29 mmol, 1.0 equiv.), potassium chloroplatinite (560 mg, 1.35 mmol, 1.05 equiv.), tetra-n-butylammonium bromide (42 mg, 0.129 mmol, 0.1 equiv.), nitrogen was purged three times, and acetic acid (80 mL) sparged with nitrogen beforehand was added. Reaction liquid nitrogenAfter bubbling with gas for 30 minutes, the reaction was stirred at room temperature for 12 hours, then at 120 ℃ for 2 days, cooled to room temperature, the solvent was distilled off under reduced pressure, stannous chloride (489 mg, 2.58 mmol, 2.0 equiv.) and methylene chloride (50 mL) were added, and the mixture was stirred at room temperature for 1 day. The reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined and the solvent was distilled off under reduced pressure. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum ether/dichloromethane = 3: 1-1: 1 to give product LC18 as a light yellow solid 721 mg, 66% yield.1H NMR (500 MHz, DMSO-d 6 ): δ 1.39 (s, 9H), 1.41 (s, 9H), 2.09 (s, 6H), 2.29 (s, 3H), 2.53 (s, 3H), 7.00 (s, 2H), 7.12 (d, J = 2.0 Hz, 1H), 7.20−7.23 (m, 2H), 7.44−7.50 (m, 2H), 7.56 (d, J = 2.0 Hz, 1H), 7.81−7.83 (m, 2H), 7.88 (d, J = 8.0 Hz, 1H), 8.12 (d, J = 2.0 Hz, 1H), 8.23 (s, 1H), 8.71 (d, J = 6.0 Hz, 1H), 9.07 (d, J = 6.0 Hz, 1H)。
Example 4: LC19 can be prepared as follows:
Figure 270389DEST_PATH_IMAGE194
Figure 315706DEST_PATH_IMAGE195
。
(1) synthesis of ligand LC 19-L: to a dry sealed tube with a magnetic rotor were added 2-Br (996 g, 3.80 mmol, 1.2 equiv.), 1-OH (1.20 g, 3.17 mmol, 1.0 equiv.), cuprous iodide (242 mg, 1.27 mmol, 40 mol%), 2-picolinic acid (313 mg, 2.54 mmol, 80 mol%) and potassium phosphate (1.35 g, 6.34 mmol, 2.0 equiv.) in that order, nitrogen was purged three times, and dimethyl sulfoxide (10 mL) was added under nitrogen protection. Placing the sealed tube in an oil bath kettle at 110 ℃ for stirring, reacting for 2 days, cooling to room temperature, washing with water, adding ethyl acetate for extraction, extracting a water layer with ethyl acetate for three times, combining organic phases, washing the organic phases with brine once, drying with anhydrous sodium sulfate, filtering, and distilling under reduced pressure to remove the solvent. Silica gel for crude productSeparating and purifying the chromatographic column, and eluting the eluent: petroleum ether/ethyl acetate = 20: 1-10: 1, yielding product LC19-L, 1.19 g as a foamy solid, yield 67%.1H NMR (500 MHz, CDCl3): δ 2.03 (s, 6H), 2.33 (s, 3H), 2.37 (s, 3H), 2.39 (s, 3H), 6.93−6.95 (m, 3H), 7.04−7.09 (m, 3H), 7.31−7.34 (m, 1H), 7.40−7.45 (m, 4H), 7.58 (d, J = 2.0 Hz, 1H), 7.62 (s, 1H), 7.88 (d, J = 8.0 Hz, 1H), 8.05−8.08 (m, 2H), 8.52 (d, J = 5.5 Hz, 1H), 8.73 (d, J= 5.0 Hz, 1H)。
(2) Synthesis of LC 19: to a 500 mL dry three-necked flask equipped with a magnetic rotor and a condenser were added LC19-L (1.15 g, 2.05 mmol, 1.0 equiv.), potassium chloroplatinite (892 mg, 2.15 mmol, 1.05 equiv.), tetra-n-butylammonium bromide (68 mg, 0.21 mmol, 0.1 equiv.), nitrogen was purged three times, and acetic acid (130 mL) previously sparged with nitrogen was added. After bubbling reaction liquid nitrogen for 30 minutes, the reaction was stirred at room temperature for 12 hours, then stirred at 120 ℃ for 2 days, cooled to room temperature, the solvent was distilled off under reduced pressure, stannous chloride (777 mg, 4.10 mmol, 2.0 equiv.) and methylene chloride (100 mL) were added, and the mixture was stirred at room temperature for 1 day. The reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, the organic phases were combined and the solvent was distilled off under reduced pressure. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum ether/dichloromethane = 5: 1-2: 1 to give product LC19 as a yellow solid 1.16 g, yield 75%.1H NMR (500 MHz, DMSO-d 6 ): δ 2.09 (s, 6H), 2.29 (s, 3H), 2.37 (s, 3H), 2.52 (s, 3H), 6.96 (dd, J = 1.5, 0.5 Hz, 1H), 7.00 (s, 2H), 7.20 (d, J = 8.0 Hz, 1H), 7.23 (dd, J = 6.0, 1.5 Hz, 1H), 7.34−7.37 (m, 1H), 7.41−7.44 (m, 1H), 7.47 (dd, J = 6.5, 1.5 Hz, 1H), 7.57 (s, 1H), 7.82 (d, J = 1.5 Hz, 1H), 7.85 (d, J = 8.0 Hz, 1H), 7.91 (d, J = 8.0 Hz, 1H), 8.12−8.13 (m, 2H), 8.71 (d, J = 6.0 Hz, 1H), 9.10 (d, J = 6.0 Hz, 1H)；
Experimental data and analysis:
Figure 789543DEST_PATH_IMAGE196
Figure 213703DEST_PATH_IMAGE197
Figure 442690DEST_PATH_IMAGE198
table 1 shows the results of the performance test of the divalent platinum metal complex (phosphorescent material) of the present invention
TABLE 1
Figure 240882DEST_PATH_IMAGE199
Note: the upper limit of the testing temperature of the melting point instrument is 320 oC。
Since the melting point of the comparative phosphorescent material PtON3 was too low to be 214.6 ‒ 215.3.3oC (see Table 1), which causes the liquid to be quickly melted into liquid during sublimation purification, and the liquid film is covered to greatly reduce the surface area and is difficult to volatilize; meanwhile, PtON3 has good planarity, serious molecular accumulation, no contribution to volatilization, and too long heating time, and decomposition occurs. As can be seen from Table 1, the phosphorescent materials of the present invention all have very high melting points and will not melt during sublimation purification; meanwhile, the introduction of alkyl and high-steric-hindrance trimethylphenyl can inhibit the accumulation of molecules, so that the molecular weight can be well increased
The emission spectrum of the green light is between 510 ‒ 530nm to maintain high luminescent color purity. As can be seen from table 1 and fig. 1 to 5, the emission spectrum of the comparative phosphorescent material PtON1Ph is significantly red-shifted to 546nm due to the phenyl group at the 4-position of pyridine and the large degree of conjugation, and the emission spectrum is very broad, with a half-peak width as large as 95nm, so that it emits yellow, which does not meet the requirement of displaying green light of three primary colors. According to the phosphorescent material, the 4-position of a pyridine ring in a molecule is introduced with the trimethylphenyl, due to the steric effect of methyl groups on two ortho-positions of the phenyl, a benzene ring and the pyridine ring tend to be vertical, the rotation of the benzene ring and the non-radiative transition generated by the rotation of the benzene ring can be inhibited, and the high quantum efficiency is favorably kept; in addition, the conjugation between the benzene ring and the pyridine ring can be eliminated, the generated red shift of the luminescence can be avoided, the wavelength of the emission spectrum is 511 ‒ 521nm, the half-peak width is small, and the requirement of green light can be met. In addition, the quantum efficiency of the divalent platinum metal complex (phosphorescent material) in a dichloromethane solution at room temperature is higher than 90%. The above data indicate that the phosphorescent materials of the present invention are ideal as green materials. Therefore, the divalent platinum metal complex molecule has certain application value in the fields of OLED display, illumination and the like;
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:
Figure 518410DEST_PATH_IMAGE200
Figure 593814DEST_PATH_IMAGE201
Figure 852757DEST_PATH_IMAGE202
Figure 685715DEST_PATH_IMAGE203
。
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:
Figure 94830DEST_PATH_IMAGE204
Figure 883795DEST_PATH_IMAGE205
。
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:
Figure 454584DEST_PATH_IMAGE206
Figure 509259DEST_PATH_IMAGE207
Figure 377858DEST_PATH_IMAGE208
Figure 834378DEST_PATH_IMAGE209
。
the electron transport layer may be formed from an organic material in combination with one or more n-type dopants (e.g., LiQ).
Organic light emitting device (bottom emitting OLED device) examples:
the structure of the bottom-emitting OLED device is that a Hole Injection Layer (HIL) is HT-1: P-3 (95:5 v/v%) on ITO-containing glass, and the thickness of the hole injection layer is 10 nanometers; the Hole Transport Layer (HTL) was HT-1, 90 nm thick; the Electron Blocking Layer (EBL) is HT-10 and has a thickness of 10 nanometers, the light emitting layer (EML) is a main material (GH-1), the platinum metal complex (95:5 v/v%) has a thickness of 35 nanometers, and the Electron Transport Layer (ETL) is ET-13: LiQ (50:50 v/v%) with a thickness of 35 nm, and then evaporation of cathode Al at 70 nm.
Figure 513753DEST_PATH_IMAGE210
The organic light emitting device was fabricated at 10mA/cm using standard methods known in the art2Voltage, efficiency and life were tested under current conditions.
Table 2 shows the performance test results of the organic light emitting devices prepared in the examples of the present invention and the comparative examples.
TABLE 2
Figure 118040DEST_PATH_IMAGE211
As shown in table 2, the device structures in the above examples and comparative examples were identical except for the light emitting layer, and based on the device performances of PtON3 and PtON1Ph as references, the devices comprising the divalent platinum metal complex of the present invention exhibited a significant improvement in current efficiency and also an improvement in lifetime as compared to conventional organic light emitting devices. 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 for 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 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 (6)

1. A divalent platinum metal complex having the structure shown in formula (I):
Figure DEST_PATH_IMAGE001
（I）
wherein the content of the first and second substances,
Ra、Rband RcEach independently represents methyl, mono-deuterated methyl, di-deuterated methyl or per-deuterated methyl;
R1、R2、R3、R4and R5Each independently is mono-, di-, tri-, tetra-, or unsubstituted; r1、R2、R3、R4And R5Each independently represents hydrogen, deuterium, alkyl of C1 ‒ C24, haloalkyl of C1 ‒ C24, cycloalkyl of C1 ‒ C24, alkoxy of C1 ‒ C24, aryl of C1 ‒ C24, heteroaryl of C1 ‒ C24Aryloxy, halogen, cycloalkenyl, heterocyclyl, alkenyl, alkynyl, hydroxy, mercapto, nitro, cyano, amino, alkylamino of mono or di C1 ‒ C24, arylamino of mono or di C1 ‒ C24, ester, nitrile, isonitrile, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxy, hydrazino, silyl or substituted silyl or polymeric groups of C1 ‒ C24, and two or more adjacent R' s1、R2、R3、R4And R5The selective linkage forms a ring.
2. The divalent platinum metal complex according to claim 1, wherein said divalent platinum metal complex has the structure of one of:
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。
3. an organic light-emitting device comprising a cathode, an anode and an organic layer, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer and an electron injection layer, wherein the organic layer comprises the divalent platinum metal complex of claim 1 or 2.
4. The organic light-emitting device according to claim 3, wherein the organic layer is a light-emitting layer further comprising a host material, wherein a volume ratio of the host material to the divalent platinum metal complex is 1: 99 to 99: 1.
5. the organic light emitting device of 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.
6. A display or lighting apparatus comprising the organic light emitting device of claim 3.
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CN108484676A (en) * 2018-01-30 2018-09-04 瑞声光电科技(常州)有限公司 The four ring gear metal platinum complexes containing 4- aryl-pyrazoles, preparation method and application
CN108276450A (en) * 2018-02-06 2018-07-13 南京工业大学 The platinum complex and its synthetic method of the tetradentate ligands coordination of aryl substitution and application
CN113201021A (en) * 2021-04-22 2021-08-03 浙江工业大学 High-radiation-rate platinum complex based on1, 8-substituted carbazole and application

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