CN106565605A - Method for preparing tri(1-phenyl-isoquinoline) iridium (III) - Google Patents

Abstract

The invention discloses a method for preparing tris(1-phenyl-isoquinoline) iridium (III) in one step. IrCl ₃ 3H ₂ O, 1-phenylisoquinoline and Na ₂ CO ₃ or K ₂ CO ₃ was added to a container with a solvent, under the condition of nitrogen protection, stirred and refluxed under microwave conditions, cooled to room temperature, filtered to obtain a solid, washed, dried and separated and purified by a chromatographic column to obtain tris(1-phenyl ‑isoquinoline) iridium (Ⅲ) pure product; the method is easy to get raw materials, high yield, simple operation, greatly shortened reaction time, simple post-reaction treatment, high product purity, low impurity content, suitable for three (1-isoquinoline) Batch production of phenyl-isoquinoline) iridium(Ⅲ).

Description

A method for preparing three (1-phenyl-isoquinoline) iridium (III)

technical field

The invention relates to a metal iridium organic complex electrophosphorescent luminescent material which can be applied in the field of electroluminescence, in particular to a method for preparing tris(1-phenyl-isoquinoline) iridium(III).

Background technique

Organic Electroluminescence Device (Organic Electroluminescence Device or Organic Light-emitting Diode, referred to as OLED), also known as light-emitting diode, is a device that uses organic materials to emit light under electric injection. It is an ideal display screen for mobile phones and color TVs. It has the advantages of all solid state, self-illumination, high brightness, wide viewing angle, thin thickness, flexible substrate, low power consumption, and wide operating temperature range. Moreover, devices based on organic materials have a simple manufacturing process, are easy to prepare in large areas, are environmentally friendly, can adopt thin-film preparation methods with low operating temperatures, and have low manufacturing costs, making OLED unique in the new generation of flat panel display technology and solid-state lighting. With comparative advantages and huge application potential, it is regarded as the latest generation of "green energy-saving" display technology and the most competitive new generation of solid-state light source.

Organic phosphorescent materials are a kind of phosphorescent materials studied earlier. In phosphorescent metal complexes, due to the introduction of heavy metal atoms, strong spin-orbit coupling will occur between the metal and the ligand, which will mix the singlet and triplet energy levels of the complex, so that the originally forbidden triplet state The transition to the ground state is realized, which greatly improves the luminous efficiency of the material. Compared with other heavy metal complexes, iridium complexes are easy to handle and easy to adjust the luminescent color, which has attracted extensive attention and research from scholars at home and abroad.

Compared with high-performance green luminescent materials, the progress of red luminescent materials is obviously lagging behind, mainly due to defects such as small energy level difference and strong charge transfer of red-emitting compounds. However, since the red luminescent material is one of the three primary color materials essential to realize full-color display, it is also a relatively scarce material nowadays, so the research on red phosphorescent materials has been very active. After several years of research, red light materials have been greatly developed, mainly divided into organic small molecule host materials, dendritic host materials and polymer host materials, due to the preparation of iridium complexes of dendritic host materials and polymer host materials It is relatively complicated, so at present, the small molecule host materials of aryl-substituted nitrogen heterocyclic compounds with iridium as the core are studied more, and many such as Ir(piq) ₃ , Ir(tiq) ₃ , Ir(fliq) ) ₃ red phosphorescent emitting materials, among which Ir(piq) ₃ is an ideal material for realizing saturated red light.

However, the synthesis of the red phosphorescent iridium complex (C^N) ₃ Ir generally adopts the method in the article published by Huo S et al. (Huo S et al. Inorganic Chemistry, 2006, 45(8):3155-7. ), first prepare intermediates such as dibromo bridge compound [(C^N) ₂ IrBr] ₂ or acetylacetone as the main ligand compound, and then react with the corresponding ligand to obtain, resulting in a large amount of raw materials required for synthesis , the synthesis reaction is more complicated, and the post-treatment is cumbersome, that is, it consumes energy and takes a long time, which is unfavorable to industrial production and hinders its application in OLEDs. Therefore, developing a new synthesis method of (C^N) ₃ Ir has extremely important academic value and practical significance to promote its application in OLED.

Contents of the invention

The object of the present invention is to provide a method for preparing three (1-phenyl-isoquinoline) iridium (III) (Ir(piq) ₃ ), which is quite different from the existing method; because the existing method Generally, two steps or more than two steps are required, which makes the synthetic reaction more complicated, and the aftertreatment is loaded down with trivial details, which consumes energy and takes a long time; and the new method of the present invention realizes the iridium phosphorescent complex Ir(piq ) ₃ by one-step synthesis, which simplifies the synthesis steps and post-treatment, reduces the amount of raw materials, significantly shortens the reaction time, and improves the reaction efficiency.

The chemical structural formula of the red-emitting iridium phosphorescent complex Ir(piq) ₃ is as follows: (CAS: 435293-93-9)

.

The method uses IrCl ₃ ·3H ₂ O as a raw material to prepare the red-emitting iridium phosphorescent complex Ir(piq) ₃ ; the synthesis steps and post-treatment are simplified, the reaction time is obviously shortened, and the reaction efficiency is improved.

The technical scheme adopted in the present invention is: add IrCl ₃ ·3H ₂ O, 1-phenylisoquinoline (piq), Na ₂ CO ₃ or K ₂ CO ₃ into a tank containing glycerol or diethylene glycol monoethyl ether Stir in a three-neck flask, under the condition of nitrogen protection, stir and reflux at microwave power 290-300W for 5-7min, cool to room temperature, filter and wash the solid with deionized water and absolute ethanol respectively to obtain the target product Ir(piq) ₃ crude product; the refining process of target product is as follows: after solid drying, use chromatographic column separation (trichloromethane is eluent), collect concentrated eluent, dry to get Ir(piq) ₃ pure product; Its chemical reaction scheme is :

.

The molar ratio of IrCl ₃ 3H ₂ O to 1-phenylisoquinoline (piq) in the step is 1:4~6; the molar ratio of IrCl ₃ 3H ₂ O to Na ₂ CO ₃ or K ₂ CO ₃ is 1:5~9.

The volume to mass ratio of glycerol or diethylene glycol monoethyl ether to IrCl ₃ ·3H ₂ O in mL:g is 20˜50:1.

Compared with the prior art, the beneficial effects of the present invention are mainly reflected in:

The synthetic method of existing organometallic iridium complex Ir(piq) ₃ generally needs the reaction of two steps or more than two steps, and first is prepared into dibromo bridge compound [(C ^ N) ₂ IrBr] ₂ or acetylacetone-based intermediates such as ligand compounds, and then react with 1-phenylisoquinoline (piq), resulting in a large amount of raw materials required for synthesis, complex synthesis reactions, and cumbersome post-processing, which consumes energy and requires more Long time; the new method of the present invention makes the synthesis of the iridium phosphorescent complex Ir(piq) ₃ of red light emission realize one-step synthesis, simplifies the synthesis steps and aftertreatment, obviously shortens the reaction time, reduces the amount of raw materials, and improves the Reaction efficiency.

detailed description

The present invention will be further described below in conjunction with specific examples, but the protection scope of the present invention is not limited thereto.

Example 1:

Weigh 5.0 g of IrCl ₃ 3H ₂ O, 11.66 g of 1-phenylisoquinoline, and 7.53 g of Na ₂ CO ₃ into a three-necked flask, add 100 mL of glycerol, and heat with microwave under nitrogen protection (power 290W) reflux for 5min, cool to room temperature, filter, wash the solid with deionized water and absolute ethanol respectively, dry the solid and separate it with silica gel column chromatography (300-400 mesh), and use chloroform as the elution The concentrated eluate was collected and dried in vacuum to obtain 11.26g Ir(piq) ₃ with a yield of 98.5%.

Characteristic structural parameters: (1) Elemental analysis: The theoretical value C,67.14%, H,3.76%, N,5.22% is consistent with the measured value C,66.89%, H,3.75%, N,5.22%; (2) Mass spectrum ( EI): m/z theoretical value: 805.21, measured value: 805.17; (3) nuclear magnetic resonance spectrum ¹ H NMR (500 MHz, CDCl ₃ ): in ppm: 8.94 (m, 3H), 8.19 (d, 3H, J = 7.8Hz), 7.71 (m, 3H), 7.60 (m, 6H), 7.34 (d, 3H, J =6.1Hz), 7.10 (d, 3H, J =6.1Hz), 6.94–6.97 (m, 6H), 6.84 (t, 3H, J = 7.4 Hz); these parameters are consistent with the chemical structure of the iridium complex Ir(piq) ₃ .

Example 2:

Weigh 5.0g of IrCl ₃ ·3H ₂ O, 13.12g of 1-phenylisoquinoline and 11.76g of K ₂ CO ₃ into a three-necked flask, add 135mL of glycerol, and heat with microwave under nitrogen protection (Power 295W) Reflux for 6min, cool to room temperature, filter, wash with deionized water and ethanol respectively, dry the obtained solid and separate it with silica gel chromatography column (300-400 mesh), chloroform as eluent, The concentrated eluate was collected and vacuum-dried to obtain 11.3 g of Ir(piq) ₃ with a yield of 98.8%.

Characteristic structural parameters: (1) Elemental analysis: The theoretical value C, 67.14%, H, 3.76%, N, 5.22% is consistent with the measured value C, 66.89%, H, 3.75%, N, 5.27%; (2) Mass spectrum ( EI): m/z theoretical value: 805.21, measured value: 805.2; (3) nuclear magnetic resonance spectrum ¹ H NMR (500 MHz, CDCl ₃ ): in ppm: 8.95 (m, 3H), 8.20 (d, 3H, J = 7.9Hz), 7.73 (m, 3H), 7.61 (m, 6H), 7.31 (d, 3H, J =6.0Hz), 7.09 (d, 3H, J =6.1Hz), 6.95–6.99 (m, 6H), 6.84 (t, 3H, J = 7.4 Hz); these parameters are consistent with the chemical structure of the iridium complex Ir(piq) ₃ .

Example 3:

Weigh out 5.0g of IrCl ₃ ·3H ₂ O, 14.57g of 1-phenylisoquinoline and 12.04g of Na ₂ CO ₃ into a three-necked flask, add 200mL of diethylene glycol monoethyl ether, under nitrogen protection conditions , heated by microwave (power 295W) and refluxed for 6min, cooled to room temperature, filtered, washed with deionized water and absolute ethanol respectively, and the obtained solid was dried and separated by silica gel column chromatography (300-400 mesh), chloroform The concentrated eluent was collected and dried in vacuum to obtain 9.91g Ir(piq) ₃ with a yield of 86.7%.

Characteristic structural parameters: (1) Elemental analysis: The theoretical value C, 67.14%, H, 3.76%, N, 5.22% is consistent with the measured value C, 67.07%, H, 3.79%, N, 5.19%; (2) Mass spectrum ( EI): m/z theoretical value: 805.21, measured value: 805.20; (3) nuclear magnetic resonance spectrum ¹ H NMR (500 MHz, CDCl ₃ ): in ppm: 8.93 (m, 3H), 8.21 (d, 3H, J = 7.9Hz), 7.75 (m, 3H), 7.61 (m, 6H), 7.28 (d, 3H, J =6.1Hz), 7.11 (d, 3H, J =6.2Hz), 6.94–6.98 (m, 6H), 6.78 (t, 3H, J = 7.2 Hz); these parameters are consistent with the chemical structure of the iridium complex Ir(piq) ₃ .

Example 4:

Weigh 5.0g of IrCl ₃ ·3H ₂ O, 14.57g of 1-phenylisoquinoline and 12.04g of Na ₂ CO ₃ into a three-necked flask, add 200mL of glycerol, and heat with microwave under nitrogen protection (Power 300W) Reflux for 7min, cool to room temperature, filter, wash with deionized water and absolute ethanol respectively, dry the obtained solid and separate it with silica gel chromatography column (300-400 mesh), chloroform is the elution solution, the concentrated eluate was collected and dried in vacuo to obtain 11.35 g Ir(piq) ₃ with a yield of 99.3%.

Characteristic structural parameters: (1) Elemental analysis: The theoretical value C, 67.14%, H, 3.76%, N, 5.22% is consistent with the measured value C, 67.11%, H, 3.74%, N, 5.22%; (2) Mass spectrum ( EI): m/z theoretical value: 805.21, measured value: 805.22; (3) nuclear magnetic resonance spectrum ¹ H NMR (500 MHz, CDCl ₃ ): in ppm: 8.96 (m, 3H), 8.17 (d, 3H, J = 7.8Hz), 7.72 (m, 3H), 7.63 (m, 6H), 7.31 (d, 3H, J =6.1Hz), 7.07 (d, 3H, J =6.1Hz), 6.94–6.99 (m, 6H), 6.82 (t, 3H, J = 7.4 Hz); these parameters are consistent with the chemical structure of the iridium complex Ir(piq) ₃ .

Example 5:

Weigh out 5.0g of IrCl ₃ ·3H ₂ O, 14.57g of 1-phenylisoquinoline and 15.68g of K ₂ CO ₃ into a three-necked flask, add 250mL of diethylene glycol monoethyl ether, under nitrogen protection conditions , microwave heating (power 300W) and reflux for 7min, after cooling to room temperature, filter, wash with deionized water and absolute ethanol respectively, and dry the obtained solid and separate it with silica gel column chromatography (300-400 mesh), trichloromethane The concentrated eluate was collected and dried in vacuum to obtain 9.56g Ir(piq) ₃ with a yield of 83.6%.

Characteristic structural parameters: (1) Elemental analysis: The theoretical value C, 67.14%, H, 3.76%, N, 5.22% is consistent with the measured value C, 67.13%, H, 3.69%, N, 5.21%; (2) Mass spectrum ( EI): m/z theoretical value: 805.21, measured value: 805.18; (3) nuclear magnetic resonance spectrum ¹ H NMR (500 MHz, CDCl ₃ ): in ppm: 8.95 (m, 3H), 8.13 (d, 3H, J = 7.6Hz), 7.76 (m, 3H), 7.59 (m, 6H), 7.33 (d, 3H, J =6.2Hz), 7.12 (d, 3H, J =6.2Hz), 6.94–6.99 (m, 6H), 6.81 (t, 3H, J = 7.4 Hz); these parameters are consistent with the chemical structure of the iridium complex Ir(piq) ₃ .

Embodiment 6:

Weigh 5.0g of IrCl ₃ ·3H ₂ O, 17.49g of 1-phenylisoquinoline and 13.55g of K ₂ CO ₃ into a three-necked flask, add 250mL of glycerol, and heat with microwave under nitrogen protection (Power 300W) Reflux for 7min, cool to room temperature, filter, wash with deionized water and absolute ethanol respectively, dry the obtained solid and separate it with silica gel chromatography column (300-400 mesh), chloroform is the elution solution, the concentrated eluate was collected and dried in vacuo to obtain 11.27g Ir(piq) ₃ with a yield of 98.6%.

Characteristic structural parameters: (1) Elemental analysis: The theoretical value C, 67.14%, H, 3.76%, N, 5.22% is consistent with the measured value C, 67.13%, H, 3.71%, N, 5.21%; (2) Mass spectrum ( EI): m/z theoretical value: 805.21, measured value: 805.18; (3) nuclear magnetic resonance spectrum ¹ H NMR (500 MHz, CDCl ₃ ): in ppm: 8.94 (m, 3H), 8.19 (d, 3H, J = 7.8Hz), 7.70 (m, 3H), 7.63 (m, 6H), 7.29 (d, 3H, J =6.1Hz), 7.08 (d, 3H, J =6.1Hz), 6.94–6.98 (m, 6H), 6.84 (t, 3H, J = 7.4 Hz); these parameters are consistent with the chemical structure of the iridium complex Ir(piq) ₃ .

Claims (3)

1. one kind prepares the method that three (1- phenyl-isoquinolin) close iridium (III), it is characterised in that：By IrCl₃·3H₂O, 1- phenyl Isoquinolin, Na₂CO₃Or K₂CO₃It is added in the container equipped with glycerol or diethylene glycol monoethyl ether, under nitrogen protective condition, 5～7min is stirred at reflux under the conditions of 290～300W of microwave power, after being cooled to room temperature, solid is filtered to obtain, is then spent respectively Ionized water, absolute ethanol washing, obtain target product crude product；With chromatography column separating purification after crude product drying, chloroform is eluting Liquid, collects concentrate eluant, obtains three (1- phenyl-isoquinolin) and close iridium (III) after being dried.

It is 2. according to claim 1 to prepare the method that three (1- phenyl-isoquinolin) close iridium (III), it is characterised in that： IrCl₃·3H₂O is 1 with 1- phenyl isoquinolin quinolines mol ratio:4～6；IrCl₃·3H₂O and Na₂CO₃Or K₂CO₃Mol ratio is 1:5～ 9。

It is 3. according to claim 1 to prepare the method that three (1- phenyl-isoquinolin) close iridium (III), it is characterised in that：The third three Alcohol or diethylene glycol monoethyl ether and IrCl₃·3H₂The volume mass of O compares mL:G is 20～50:1.