CN116606281A - Homoleptic platinum metal liquid crystal luminescent material containing triazole pyridine derivative and synthesis and application thereof - Google Patents

Homoleptic platinum metal liquid crystal luminescent material containing triazole pyridine derivative and synthesis and application thereof Download PDF

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CN116606281A
CN116606281A CN202310449503.6A CN202310449503A CN116606281A CN 116606281 A CN116606281 A CN 116606281A CN 202310449503 A CN202310449503 A CN 202310449503A CN 116606281 A CN116606281 A CN 116606281A
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liquid crystal
platinum
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triazole pyridine
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温庭斌
邹果
廖璟
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Xiamen University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract

Homoleptic platinum metal liquid crystal luminescent material containing triazole pyridine derivative and synthesis and application thereof. The platinum complex takes triazole pyridine derivatives with flexible long chains as ring metal homoligands, and the polyazole is introduced into the ligands to assist the electron transmission of the materials, so that the hole and electron transmission capacity of the platinum complex are balanced. The platinum complex is doped into 4,4 '-tris (carbazole-9-yl) triphenylamine (TCTA) and 2,2' - (1, 3-phenyl) bis [5- (4-tert-butylphenyl) -1,3, 4-oxadiazole ] (OXD-7) according to different mass concentrations to serve as a light-emitting layer, so that a single doped solution processing type organic light-emitting diode (OLED) is prepared, and a high-efficiency white light and orange red light device is obtained, so that the application of the OLED in a display and illumination system is further expanded.

Description

Homoleptic platinum metal liquid crystal luminescent material containing triazole pyridine derivative and synthesis and application thereof
Technical Field
The invention relates to the field of organic electroluminescent materials, in particular to a homoleptic platinum metal liquid crystal luminescent material containing triazole pyridine derivatives, and synthesis and application thereof.
Background
The metal liquid crystal luminescent material contains metal cationsA liquid crystal material; the introduction of heavy atoms enhances the spin-orbit coupling (SOC) of the molecules, so that the intersystem crossing probability (ISC) of the molecules is enhanced, and the excited triplet state T is increased 1 To give off light efficiently or to greatly increase the light quantum yield of the molecule (Xiao, l.; chen, z.; qu, b.; luo, j.; kong, s.; gong, q.; kido, J.Adv.Mater.2011,23,926;Choy,W.C.; chan, w.k.; yuan, y.adv. Mate. 2014,26,5368).
Meanwhile, most of the metallic liquid crystal luminescent materials contain a plurality of flexible long chains except for very few metallic liquid crystal luminescent materials (Krikorian, m.; liu, s.; swager, t.m.j.am.chem.soc.2014,136, 2952) or contain one flexible chain (Geng, h.; luo, k.; cheng, h.; zhang, s.; ni, h.; wang, h.; yu, w.; li, q.rsc adv.2017,7,11389), so that they generally have good solubility in common organic solvents, which is advantageous for the preparation of solution processed OLEDs.
On the other hand, white organic electroluminescent devices (WOLEDs) have great potential application in the field of large-area flexible display and lighting systems, whereas solution-processed OLEDs can be formed into films using low-cost and process-reduced solution processing methods. The light-emitting active molecules used in WOLEDs are typically single-doped and multi-component doped (the latter comprising two dopants with complementary color light and a three-component dopant with red, green, and blue light materials, respectively). The preparation process of the multi-component doped white light OLED device is more complex, the preparation process of the single doped white light OLED device is simpler, and the single doped active luminescent molecules with wide wavelengths can cover the whole luminescent area. However, most platinum metal liquid crystals emit light in yellow-green or yellow (Wu, x.; zhu, m.; bruce, d.w.; zhu, w.; wang, y.j. Mater.chem.c 2018,6,9848.;), while their luminescence in the aggregated state is typically yellow or orange-red (Cuerva, c.; cano, m.; lodeiro, c.chem.rev.2021,121, 12966), making it difficult to formulate white light for their luminescence at different doping concentrations. While combining highly efficient blue and yellow light emitting materials will result in optimal white light efficiency (Liang, a.; huang, g.; dong, s.; zheng, x.; zhu, j.; wang, z.; wu, w.; zhang, j.; huang, f.j. Match. Chem. C2016,4,6626). It is therefore of particular importance to find platinum complexes in which the monomer molecules emit blue light and their excimer can emit yellow or orange-red light.
On the other hand, the performance of the currently reported platinum-containing metal liquid crystal luminescent materials in white and high-efficiency orange-red OLEDs is generally low (as demonstrated by lower external quantum efficiency EQE; wang, y.; fan, j.; shi, j.; qi, h.; baranoff, e.; xie, g.; li, q.; tan, h.; liu, y.; zhu, w.dyes Pigments 2016,133,238). Considering that the platinum liquid crystal complex itself has a better hole transporting ability (Zou, g.; zhao, l.; zeng, l.; luo, k.; ni, h.; wang, h.; li, q.; yu, w.; li, x.inorg. Chem.2019,58,861), electron transport of the target molecule will be facilitated by the introduction of a ligand containing a nitrogen atom with a stronger electrophilic potential than a carbon atom, making recombination of holes and electrons in the luminescent molecule more beneficial, thereby improving its electroluminescent efficiency. While the conventional neutral platinum homoligands based on the pyridine derivatives of triazole are ligands with more nitrogen atoms, only one report (Prabhath, M.R.R.; romanova, J.; curry, R.J.; silva, S.R.P.; jarowski, P.D. Angew.chem.int.ed.Engl.,2015,54,7949) has been reported, and the reported homoplatinum homocomplexes of these pyridine ligands have a disadvantage of poor solubility, since they have not been applied to the preparation of light emitting devices. Therefore, the application research of the triazole homoplatinum complex on the organic electroluminescent device is still blank. The invention introduces 3,4, 5-position on the pyridine ring of the ring metal ligand triazole pyridine with flexible alkoxy long chain modified phenyl ， The homoplatinum complex with the triazole pyridine as the core is optimized, and is applied to OLEDs.
Disclosure of Invention
The invention aims at synthesizing a metal liquid crystal luminescent material which is matched with cycloplatin and takes triazole pyridine derivatives with peripheral flexible long chains as ligands; the platinum complexes are used as single doped luminescent active molecules to prepare the high-efficiency white light and orange red light organic electroluminescent device.
The invention is characterized in that the platinum complex takes triazole pyridine with flexible long chain as a cyclometalated ligand; on the basis of the existing platinum metal complex with hole-transporting capability, the triazole pyridine with electron-transporting property is introduced.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the chemical structure of the cycloplatinum homoleptic metal liquid crystal luminescent material taking the triazole pyridine derivative as a ligand is as follows:
the types of the peripheral flexible chains are as follows:
1) n=3, the flexible chain is n-propyl;
2) n=4, the flexible chain is n-butyl;
3) When n=6, the flexible chain is n-hexyl;
4) When n=8, the flexible chain is n-octyl;
5) When n=10, the flexible chain is n-decyl;
6) When n=12, the flexible chain is n-dodecyl.
The platinum complex of the invention takes triazole pyridine with a flexible long chain as a cyclometalated ligand, a platinum source is potassium chloroplatinite, a solvent is a mixture of tetrahydrofuran, glycol diethyl ether, methanol and other organic solvents and water according to a certain proportion (1:1-10:1), weak base such as potassium carbonate, sodium carbonate and the like are taken as proton removing reagents, the reaction temperature is between room temperature and 100 ℃, and the reaction time is between 12 and 24 hours.
The application of the homoplatinum metal liquid crystal luminescent material containing the triazole pyridine derivative is used for preparing luminescent devices, wherein Pt-TC8 and Pt-TC10 are particularly used for white light devices and orange red light devices, and the white light devices and the orange red light devices comprise ITO, a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and an aluminum metal cathode.
The platinum complex in the device is used as a luminescent molecule; the mass concentration of the complex serving as the doping agent is 0.2% -60%; the blending main body comprises 0.5-1.5 of 4,4 '-tris (carbazole-9-yl) triphenylamine (TCTA) and 2,2' - (1, 3-phenyl) bis [5- (4-tert-butylphenyl) -1,3, 4-oxadiazole ] (OXD-7) according to the mass ratio; specifically, the light-emitting layer in the white light device is formed by doping the platinum complex as a single dopant into TCTA and OXD-7; the mass concentration of the single dopant doping is 0.2% -1.5%.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1) The platinum-ring metal liquid crystal luminescent materials of Pt-TC8 and Pt-TC10 which take the triazole pyridine derivative as a ligand have excellent electron transmission characteristics, so that the electron injection and electron transmission properties of the platinum complex in the device can be effectively improved;
2) The solubility of the platinum complex is greatly improved by grafting a plurality of flexible long chains on the periphery of the homoplatinum metal liquid crystal luminescent molecules of the triazole pyridine derivative, and the preparation of the solution processing type organic luminescent device is facilitated;
3) The platinum complex is used as a single doping agent, and the doping concentration is 0.2 to 1.5 weight percent, so that the platinum complex can be used for preparing a white light device; at a doping concentration of 1wt%, the white light OLEDs device performance reached an optimum (maximum external quantum efficiency of 5.08%) and was currently based on platinum liquid crystal complexes (Wang, y.; fan, j.; shi, j.; qi, h.; baranoff, e.; xie, g.; li, q.; tan, h.; liu, y.; zhu, w.dyes Pigments,2016,133,238; wang, y.; fan, j.; li, t.; wang, q.; shi, j.; qu, z.; tan, h.; liu, y.; zhu, w.rsc ad v.; 2016,6,45864; yau, x.; wu, x.; zhou, d.; yu, j.; yu, y.; bru, g, 62, d..62, d..n.
4) The doping concentration of the platinum complex is increased to 10 to 60 weight percent, and the high-efficiency orange-red light device can be obtained. When the doping concentration is 10wt%, the maximum external quantum efficiency of the prepared orange-red OLED is 20.24%, which is comparable to the reported high-performance orange-red OLEDs (eqe≡20%) (Chen, j. —x.); tao, w. -w; the OLED is also an OLED (currently reported to be a metal liquid crystal-based OLEDs E of up to 11.3%, qian, G, yang, X, wang, X, hed, J, W, 62. U.S.; U.S.) which is the best performing OLED.
Drawings
FIG. 1 is a graph of the ultraviolet-visible absorption spectrum of a platinum complex Pt-TC8 in methylene chloride solution;
FIG. 2 is a photoluminescence spectrum of a platinum complex Pt-TC8 in a dichloromethane solution;
FIG. 3 is a photoluminescence spectrum of a platinum complex Pt-TC8 in the solid state;
FIG. 4 is a photoluminescence spectrum of a platinum complex Pt-TC8 in the liquid crystalline state;
FIG. 5 is a thermogravimetric analysis (TGA) spectrum of the platinum complex Pt-TC 8;
FIG. 6 is a birefringent texture (POM) diagram of a platinum complex Pt-TC 8;
FIG. 7 is an X-ray diffraction (XRD) pattern of the platinum complex Pt-TC 8;
FIG. 8 is an energy level of device structures and related materials for platinum complexes Pt-TC8 and Pt-TC 10;
FIG. 9 is an electroluminescent spectrum of the device with a Pt-TC8 doping concentration of 1wt% for the platinum complex;
FIG. 10 is a graph of current density vs. voltage vs. luminance for a device with a Pt-TC8 doping concentration of 1wt% for a platinum complex;
FIG. 11 is a graph showing the current and power efficiency of the device as a function of luminance at a Pt-TC8 doping concentration of 1 wt%;
FIG. 12 is a graph of external quantum efficiency and brightness for a device with a Pt-TC8 doping concentration of 1 wt.% for a platinum complex;
FIG. 13 is an electroluminescent spectrum of the device with a Pt-TC8 doping concentration of 10wt% for the platinum complex;
FIG. 14 is a graph of current density vs. voltage vs. luminance for a device with a Pt-TC8 doping concentration of 10wt% for a platinum complex;
FIG. 15 is a graph showing the current and power efficiency of the device as a function of luminance at a doping concentration of 10wt% for the Pt-TC8 platinum complex;
FIG. 16 is a graph of external quantum efficiency and luminance of a device at a Pt-TC8 doping concentration of 10 wt%.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the invention more clear and obvious, the invention is further described in detail below with reference to the accompanying drawings and examples, and specifically comprises synthesis, characterization, preparation and testing of target molecules.
Example 1
Synthesis of 2- (5-1, 2, 3-triazolyl) -5- (3, 4, 5-trioctyloxy) phenyl-pyridine
1) Synthesis of 3,4, 5-trihydroxybromide benzene
To a 100mL branched single neck round bottom flask was added dichloromethane (DCM, 15 mL) and 3,4, 5-trimethoxybromobenzene (3 g,12.14 mmol), argon was purged 3 times and placed in a cold trap at-78deg.C and stirred for 15min. To this solution was then added dropwise a dichloromethane solution of boron tribromide (10.00g,40.06mmol;in 5mL DCM) for 30min. After the addition was completed, the reaction flask was removed from the cold trap, allowed to naturally return to room temperature and stirred overnight. The reaction solution was then poured into a beaker containing a large amount of ice-water mixture (100 mL) and extracted three times with Ethyl Acetate (EA) (3X 50 mL). The combined organic layers were dried over anhydrous sodium sulfate and suction filtered, and the resulting filtrate was subjected to rotary evaporation in a low pressure water bath to remove the organic solvent and give 3,4, 5-trihydroxybromide benzene as an off-white solid (2.35 g, 94%)
2) Synthesis of 3,4, 5-tris (n-octyloxy) bromobenzene
To a 200mL branched eggplant-shaped single necked flask were added 3,4, 5-trihydroxybromide (2.00 g,9.76 mmol), 1-bromo-n-octane (6.22 g,32.21 mmol) and potassium carbonate (8.09 g,58.56 mmol), and after three argon substitutions, 30mL of N, N-Dimethylformamide (DMF) was added. The sealed eggplant-shaped bottle is placed in an oil bath pot at 80 ℃ for reaction for 36h. After the reaction was completed, the temperature was lowered to room temperature, 100mL of water was added to the reaction flask, and the mixture was extracted three times with DCM (3X 20 mL). The organic layers were combined again, dried over anhydrous sodium sulfate and suction filtered, the organic solvent was removed by rotary evaporation from the resulting filtrate in a low pressure water bath, the crude product obtained was purified by column chromatography on silica gel (200-300 mesh) with Petroleum Ether (PE)/ea=20:1 (v/v) to give 3,4, 5-tris (n-octyloxy) bromobenzene as a white solid (4.76 g, 90%). 1 H NMR(500MHz,CDCl 3 )δ6.67(s,2H),3.93(t,J＝6.3Hz,4H),3.90(t,J＝6.3Hz,2H),1.79(quintet,J＝7.0Hz,4H),1.72(quintet,J＝7.0Hz,2H),1.45(quintet,J＝7.2Hz,6H),1.36-1.25(m,24H),0.89(t,J＝6.5Hz,9H).
3) Synthesis of 3,4, 5-tri (n-octyloxy) phenylboronic acid pinacol ester
Into a 200mL branched eggplant-shaped single necked flask were charged 3,4, 5-tris (n-octyloxy) bromobenzene (3.00 g,5.54 mmol), pinacol biborate (1.69 g,6.65 mmol), potassium acetate (1.63 g,16.62 mmol), 1, 4-dioxane (70 mL) and Pd (dppf) Cl 2 ·CH 2 Cl 2 (228 mg,0.28 mmol). The sealed eggplant-shaped bottle is placed in an oil bath pot at 85 ℃ for reaction for 24 hours. After the reaction was completed, the temperature was lowered to room temperature, and then the reaction solution was poured into a beaker containing water (100 mL) and extracted three times with DCM (3×50 mL). Combining the organic layers, drying with anhydrous sodium sulfate, suction filtering, rotary evaporating the obtained filtrate in low pressure water bath to remove organic solvent, purifying the crude product with silica gel (200-300 mesh) column chromatography, eluting with PE/EA=15:1 (v/v), and obtaining 3,4, 5-tri (n-octane)Oxy) pinacol ester of phenylboronic acid was a tan waxy solid (2.64 g, 81%). 1 H NMR(500MHz,CDCl 3 )δ6.99(s,2H),4.01(t,J＝6.5Hz,4H),3.97(t,J＝6.5Hz,2H),1.79(quintet,J＝7.1Hz,4H),1.74(quintet,J＝7.1Hz,2H),1.46(quintet,J＝7.4Hz,6H),1.33(s,12H),1.34-1.25(m,24H),0.884(t,J＝6.8Hz,6H),0.879(t,J＝6.8Hz,3H)。
4) Synthesis of 5-bromo-2- ((isopropyl silicon-based) ethynyl) pyridine
Into a 200mL branched eggplant-shaped single-necked flask were charged 2-iodo-3-bromopyridine (10 g,35.22 mmol), tris (isopropyl) silylacetylene (6.49 g,35.57 mmol), pd (PPh) 3 ) 2 Cl 2 (1.24 g,1.76 mmol) and cuprous iodide (335 mg,1.76 mmol), triethylamine (TEA, 60 mL) and acetonitrile (MeCN, 60 mL) were added after three argon substitutions, and after 12h reaction at room temperature, the solvent was removed by rotary evaporation. DCM (100 mL) was added to the solid mixture, the organic layer was dried over anhydrous sodium sulfate and suction filtered three times (3X 50 mL), the organic solvent was removed by rotary evaporation in a low pressure water bath, and the crude product was purified by column chromatography on silica gel (200-300 mesh) eluting with n-hexane to give 5-bromo-2- ((isopropyl silyl) ethynyl) pyridine as a colorless oil (11.92 g, 100%). 1 H NMR(500MHz,CDCl 3 )δ8.63(dd,J＝2.3,0.6Hz,1H),7.76(dd,J＝8.3,2.4Hz,1H),7.34(dd,J＝8.3,0.7Hz,1H),1.15–1.12(m,21H)
5) Synthesis of 5- ((3, 4, 5-trioctanoxy) phenyl) -2- ((isopropyl silicon-based) ethynyl) pyridine
To a 100mL branched reaction tube were added 3,4, 5-tris (n-octyloxy) phenylboronic acid pinacol ester (2.50 g,4.25 mmol), 5-bromo-2- ((isopropyl-silyl) ethynyl) pyridine (1.44 g,4.25 mmol), potassium carbonate (1.76 g 12.75 mmol) and tetrakis (triphenylphosphine) palladium ((Pd (PPh) 3 ) 4 ) And (3) extracting and replacingAfter argon gas was added three times, toluene (30 mL), ethanol (15 mL) and water (15 mL) were added sequentially to the reaction tube, followed by reflux reaction with heating for 24h. After completion of the reaction, the reaction solution was cooled to room temperature, poured into water (200 mL) and extracted three times with DCM (3×50 mL), the organic layers were combined, dried over anhydrous sodium sulfate and suction filtered, the resulting filtrate was subjected to rotary evaporation in a low pressure water bath to remove the organic solvent, and the resulting crude product was purified by column chromatography on silica gel (200-300 mesh) with PE/ea=30:1 (v/v) as a eluent to give 5- ((3, 4, 5-trioctanoxy) phenyl) -2- ((isopropyl-silylethynyl) pyridine as a white solid (2.64 g, 86%). 1 H NMR(500MHz,CDCl 3 )δ8.76(s,1H),7.79(d,J＝7.1Hz,1H),7.51(d,J＝8.1Hz,1H),6.71(s,2H),4.03(t,J＝6.5Hz,4H),3.99(t,J＝6.5Hz,2H),1.83(quintet,J＝7.1Hz,4H),1.77(quintet,J＝7.1Hz,2H),1.49(quintet,J＝7.3Hz,6H),1.38–1.26(m,24H),1.19-1.13(m,21H),0.88(t,J＝6.7Hz,9H)
6) Synthesis of 5- ((3, 4, 5-trioctanoxy) phenyl) -2-ethynylpyridine
To a 100mL single-necked flask was added 5- ((3, 4, 5-trioctanoxy) phenyl) -2- ((isopropyl silicon-based) ethynyl) pyridine (2.00 g,2.78 mmol), tetrabutylammonium fluoride (TBAF 1.09g,4.17 mmol), tetrahydrofuran (THF) and methanol (MeOH 2 mL), and the reaction was followed by a thin layer chromatography spot plate under an air atmosphere at room temperature, and after 5min, the reaction was completed. The solvent was removed by rotary evaporation and the crude product purified by column chromatography over silica gel (200-300 mesh) eluting with PE/ea=10:1 (v/v) to give 5- ((3, 4, 5-trioctanoxy) phenyl) -2-ethynylpyridine as a white solid (1.55 g, 99%). 1 H NMR(500MHz,CDCl 3 )δ8.78(s,1H),7.84(d,J＝7.8Hz,1H),7.55(d,J＝8.0Hz,1H),6.73(s,2H),4.03(t,J＝6.5Hz,4H),4.00(t,J＝6.5Hz,2H),3.25(s,1H),1.83(quintet,J＝6.9Hz,4H),1.77(quintet,J＝6.9Hz,2H),1.49(quintet,J＝7.1Hz,6H),1.37-1.27(m,24H),0.88(t,J＝6.8Hz,9H)。
7) Synthesis of azidomethyl pivalate
To a 500mL single-necked flask was added sodium azide (NaN 3 20.00g,307.64 mmol) and chloromethyl pivalate (42.12 g,279.68 mmol), argon was purged three times and deionized water (160 mL) was added. After the reaction was completed, the reaction was cooled to room temperature, the reaction solution was extracted three times with EA (3×100 mL), the combined organic layers were dried over anhydrous sodium sulfate and suction-filtered, and the filtrate was distilled off to remove the solvent to give methyl pivalate as a colorless liquid (35.00 g, 80%). 1 H NMR(500MHz,CDCl 3 )δ5.14(s,2H),1.25(s,9H)。
8) Synthesis of methyl 1-pivalate-4- (2- (5- ((3, 4, 5-trioctanoxy) benzene)) pyridyl) -1,2, 3-triazole
To a 100mL single-necked flask was added 5- ((3, 4, 5-trioctyloxy) phenyl) -2-ethynylpyridine (1.25 g,2.22 mmol), azidomethyl pivalate (523 mg,3.33 mmol), THF (15 mL), copper sulfate pentahydrate (28 mg,0.11 mmol), sodium ascorbate (145 mg,0.73 mmol), deionized water (5 mL), and t-butanol (1 mL). After completion of the reaction, the reaction mixture was extracted three times with EA (3×20 mL) and the combined organic layers were washed three times with water (3×50 mL), dried over anhydrous sodium sulfate and suction filtered to give the crude product, which was purified by column chromatography on silica gel (200-300 mesh) with PE/ea=4:1 (v/v) to give methyl 1-pivalate-4- (2- (5- ((3, 4, 5-trioctanoxy) benzene)) pyridinyl) -1,2, 3-triazole as a white waxy solid (1.41 g, 88%). 1 H NMR(500MHz,CDCl 3 )δ8.79(s,1H),8.42(s,1H),8.22(d,J＝7.8Hz,1H),7.94(d,J＝8.0Hz,1H),6.77(s,2H),6.32(s,2H),4.05(t,J＝6.5Hz,4H),4.00(t,J＝6.5Hz,2H),1.83(quintet,J＝7.1Hz,4H),1.77(quintet,J＝7.1Hz,2H),1.49(quintet,J＝7.4Hz,6H),1.36-1.26(m,24H),1.21(s,9H),0.89(t,J＝7.0Hz,3H),0.88(t,J＝7.0Hz,6H)。
9) Synthesis of 2- (5-1, 2, 3-triazolyl) -5- (3, 4, 5-trioctyloxy) phenyl-pyridine
To a 100mL single-necked flask was added methyl 1-pivalate-4- (2- (5- ((3, 4, 5-trioctanoxy) benzene)) pyridinyl) -1,2, 3-triazole (800 mg,1.11 mmol), THF (15 mL), and MeOH (5 mL), and potassium hydroxide solution (KOH, 137mg,2.44mmol;2M in water). After completion of the reaction at room temperature for 15min under air atmosphere and TLC detection, the reaction solution was extracted three times with EA (3X 20 mL), the combined organic layers were washed three times with water (3X 20 mL), dried over anhydrous sodium sulfate and suction filtered to give 4- (2- (5- ((3, 4, 5-trioctanoxy) phenyl)) pyridinyl) -1,2, 3-triazole as a grey viscous solid (432 mg, 64%). The product of the step can be used for feeding in the next reaction without further purification.
Example 2
Synthesis of Complex Pt-TC8
To a 100mL reaction tube were added 2- (4-1, 2, 3-triazolyl) -5- (3, 4, 5-trioctyloxy) phenyl-pyridine (200 mg,0.32 mmol), potassium tetrachloroplatinate (K) 2 PtCl 4 66mg,0.16 mmol), sodium carbonate (102 mg,0.96 mmol), ethylene glycol monoethyl ether (3 mL), and deionized water (1 mL). Under argon atmosphere, the mixture was stirred in an oil bath at 60℃for 10min. Then the temperature was raised to 100℃for 24h, after the reaction was completed, the temperature was lowered to room temperature, the combined organic layers were dried with DCM (3X 20 mL), suction filtered to give a crude product, which was purified by column chromatography on silica gel (200-300 mesh) eluting with DCM/THF=2:1 (v/v) to give complex Pt-TC8 as an orange viscous solid (195 mg, 85%). 1 H NMR(500MHz,CDCl 3 )δ10.40(s,2H),7.79(d,J＝8.2Hz,2H),7.66(s,2H),7.28(d,J＝8.2Hz,2H),6.74(s,4H),4.07(t,J＝6.2Hz,8H),4.03(t,J＝6.5Hz,4H),1.88(quintet,J＝7.0Hz,8H),1.81(quintet,J＝7.1Hz,4H),1.59-1.50(m,12H),1.43-1.31(m,48H),0.92(t,J＝6.0Hz,6H),0.91(t,J＝6.0Hz,12H). 13 CNMR(126MHz,CDCl 3 ) Delta 153.64,150.84,149.24,144.08,138.97,135.38,134.55,131.03,128.91,118.67,104.18,73.56,69.24,32.00,31.97,30.54,29.70,29.65,29.48,29.47,26.35,26.25,22.75,14.14 theoretical calculated value of elemental analysis: c (C) 74 H 114 N 8 O 6 Pt is C,63.18; h,8.17; n,7.96; actual measurement: c,63.28; h,8.24; n,7.98.
Photophysical and liquid crystalline Properties of the Complex Pt-TC 8:
an ultraviolet-visible absorption spectrum of the platinum complex Pt-TC8 in dichloromethane solution (fig. 1) shows two main absorption bands of 258-361 and 361-426 nm respectively, the former being assigned to the charge transfer transition of pi-pi in the ligand; the latter is attributed to the charge transfer transitions between metal to ligand (MLCT) and within ligand (ILCT). Photoluminescence spectra of the platinum complex Pt-TC8 in methylene chloride solution (fig. 2) gave a maximum emission wavelength of 492nm, derived from the monomer complex luminescence. Photoluminescence spectra of the platinum complex Pt-TC8 in the solid state (fig. 3) with a maximum emission wavelength of 622nm was attributed to the charge transfer transition of the metal-ligand (MMLCT). The photoluminescence spectrum of the platinum complex Pt-TC8 in the liquid crystalline state (fig. 4) had a maximum emission wavelength of 624nm, also attributed to MMLCT. Thermogravimetric analysis (TGA) profile (fig. 5) of the platinum complex Pt-TC8 indicated a thermal decomposition temperature of 340 ℃. A birefringence texture (POM) map of the platinum complex Pt-TC8 (fig. 6), exhibiting a fan-shaped texture; the X-ray diffraction (XRD) spectrum of the Pt-TC8 complex (FIG. 7) had five sets of peaks with a spacing ratio satisfying 1:1/. Cndot.3:1/2:1/. Cndot.7:1/3, indicating a hexagonal columnar liquid crystal structure.
Example 3
Preparation of white light device using platinum complex as doping material and device test thereof
Referring to FIG. 8, the white light device structure was ITO/PEDOT: PSS (50 nm)/Poly-TPD (30 nm)/99 wt% TCTA: OXD-7 (1:1): 1wt% Pt-TC8/BmPyPb (50 nm)/LiF (1 nm)/Al (100 nm).
Wherein ITO is indium tin oxide, PEDOT is PSS is Poly (3, 4-ethylenedioxythiophene) -Poly (styrenesulfonic acid), poly-TPD is Poly [ bis (4-phenyl) (4-butylphenyl) amine, TCTA is 4,4 '-tris (carbazol-9-yl) triphenylamine, OXD-7 is 2,2' - (1, 3-phenyl) bis [5- (4-tert-butylphenyl) -1,3, 4-oxadiazole ], bmPyPb is 1, 4-bis (3, 5-bis (3-pyridyl) phenyl) benzene.
Firstly, respectively cleaning an Indium Tin Oxide (ITO) glass substrate by using a glass detergent, acetone, isopropanol and deionized water in sequence in an ultrasonic process, and then drying the solvent. PEDOT PSS was spin-coated onto the pretreated ITO substrate after microfiltration with 0.22 μm and dried at 130℃for 15min to form a hole injection layer of 50nm thickness. A chlorobenzene solution of Poly-TPD was spin-coated onto PEDOT: PSS to give a hole transport layer (30 nm in thickness). TCTA, OXD-7 and Pt-TC8 are mixed according to the mass ratio of 49.5 percent: 49.5%:1% in DCM (5 mg mL) -1 ) A50 nm thick light-emitting layer was prepared by spin-coating a hole transport layer after filtration through a 0.22 μm microporous membrane. Then, from the reference point, is inferior to 4.0X10 -4 BmPyPb, lithium fluoride and aluminum are respectively evaporated on the light-emitting layer as an electron transport layer, an electron injection layer and a metal cathode under Pa conditions, and the thicknesses of the BmPyPb, the lithium fluoride and the aluminum are respectively 50nm, 1nm and 100nm. Their current density-voltage-brightness properties were measured on a Keithley 2400source meter and calibrated silicon photodiodes. The electroluminescence spectrum was measured by HORIBA Jobin-Yvon FluoMax-4 fluorescence spectrometer.
The electroluminescent spectrum of a Pt-TC8 based single doped (1 wt%) electroluminescent device is shown in fig. 9, with a maximum emission wavelength of 567nm and a full width at half maximum of 204nm. The current density-voltage-luminance of the device is shown in fig. 10, indicating an on-voltage of 3.40V. The current efficiency and power efficiency curves are shown in FIG. 11, and the maximum current efficiency and power efficiency are 11.7cd A respectively -1 And 9.4lm W -1 . The maximum luminous brightness is 1220cd m -2 . The external quantum efficiency spectrum is shown in fig. 12, and the maximum external quantum efficiency is 5.08%. The CIE coordinates were (0.35,0.38), very close to the CIE coordinates of standard white light (0.33 ).
Example 4
Preparation of orange-red light device using platinum complex as doping material and device test thereof
The orange red device structure was ITO/PEDOT: PSS (50 nm)/Poly-TPD (30 nm)/90 wt% TCTA: OXD-7 (1:1): 10wt% Pt-TC8/BmPyPb (50 nm)/LiF (1 nm)/Al (100 nm).
The relevant materials used were similar to those of example 3.
Firstly, respectively cleaning an Indium Tin Oxide (ITO) glass substrate by using a glass detergent, acetone, isopropanol and deionized water in sequence in an ultrasonic process, and then drying the solvent. PEDOT PSS was spin-coated onto the pretreated ITO substrate after microfiltration with 0.22 μm and dried at 130℃for 15min to form a hole injection layer of 50nm thickness. A chlorobenzene solution of Poly-TPD was spin-coated onto PEDOT: PSS to give a hole transport layer (30 nm in thickness). TCTA, OXD-7 and Pt-TC8 are mixed according to a mass ratio of 45%:45%:10% in DCM (5 mg mL) -1 ) A50 nm thick light-emitting layer was prepared by spin-coating a hole transport layer after filtration through a 0.22 μm microporous membrane. Then, from the reference point, is inferior to 4.0X10 -4 BmPyPb, lithium fluoride and aluminum are respectively evaporated on the light emitting layer as an electron transporting layer, an electron injecting layer and a metal cathode under Pa, and their thicknesses are respectively 50, 1 and 100nm. Their current density-voltage-brightness properties were measured on a Keithley 2400source meter and calibrated silicon photodiodes. The electroluminescence spectrum was measured by HORIBA Jobin-Yvon FluoMax-4 fluorescence spectrometer.
The electroluminescent spectrum of a Pt-TC8 based single doped (10 wt%) electroluminescent device is shown in fig. 13, with a maximum emission wavelength of 615nm and a full width at half maximum of 91nm. The current density-voltage-luminance of the device is shown in fig. 14, indicating an on-voltage of 3.40V. The current efficiency and power efficiency curves are shown in FIG. 15, and the maximum current efficiency and power efficiency are 40.3cd A respectively -1 And 23.0lm W -1 . The maximum luminous brightness is 11592cd m -2 . The external quantum efficiency spectrum is shown in fig. 16, and the maximum external quantum efficiency is 20.24%. The CIE coordinates are (0.57,0.42), which are typical orange-red chromaticity coordinates.

Claims (10)

1. The homoleptic platinum metal liquid crystal luminescent material containing the triazole pyridine derivative is characterized in that a triazole pyridine unit with electron transport capability is introduced on the basis of a platinum metal complex with hole transport capability, and the structural formula is as follows:
2. the synthesis of homoleptic platinum metal liquid crystal luminescent material containing triazole pyridine derivative as claimed in claim 1, characterized in that: organic solvent and water are used as mixed solvent, weak base is used as proton removing reagent, and triazole pyridine with flexible long chain is used as ring metal ligand to react with platinum source at a certain temperature.
3. The synthesis of claim 2, wherein: the platinum source comprises potassium chloroplatinite; the organic solvent comprises at least one of tetrahydrofuran, ethylene glycol diethyl ether and methanol.
4. The synthesis of claim 2, wherein: the weak base comprises at least one of potassium carbonate and sodium carbonate.
5. The synthesis of claim 2, wherein: the volume ratio of the organic solvent to the water is 1:1-10:1.
6. The synthesis of claim 2, wherein: the reaction temperature is between room temperature and 100 ℃; the reaction time is 12-24 h.
7. The application of the homoleptic platinum metal liquid crystal luminescent material containing the triazole pyridine derivative as claimed in claim 1, which is characterized in that: is applied to a light emitting device.
8. The use according to claim 7, wherein: pt-TC8 and Pt-TC10 were used to make white light devices and orange-red light devices.
9. The use according to claim 7, wherein: the light emitting device includes an Indium Tin Oxide (ITO) anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and an aluminum metal cathode, which are sequentially disposed.
10. The use according to claim 7, wherein: in the luminescent device, a homoplatinum metal liquid crystal luminescent material containing a triazole pyridine derivative is doped into 4,4 '-tris (carbazole-9-yl) triphenylamine (TCTA) and 2,2' - (1, 3-phenyl) bis [5- (4-tert-butylphenyl) -1,3, 4-oxadiazole ] (OXD-7) to form a luminescent layer, wherein the doped mass concentration is 0.2% -60%; the mass ratio of TCTA to OXD-7 is 0.5-1.5.
CN202310449503.6A 2023-04-24 2023-04-24 Homoleptic platinum metal liquid crystal luminescent material containing triazole pyridine derivative and synthesis and application thereof Pending CN116606281A (en)

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