CN113563386A - A kind of iridium metal complex and its application - Google Patents

Abstract

_The invention discloses _an iridium metal complex and _an application thereof, belonging to the technical field of organic light _- emitting materials. Deuterium, halogen, cyano, substituted or unsubstituted C ₁ -C ₈ alkyl, substituted or unsubstituted C ₆ -C ₁₀ aryl, substituted or unsubstituted 4-8 membered aromatic heterocyclic group. After the iridium metal complex with the novel structure provided by the invention is applied to an organic electroluminescence device, the luminous efficiency and the service life of the device can be improved. In addition, the preparation method of the iridium metal complex provided by the present invention has simple preparation steps and high product purity.

Description

A kind of iridium metal complex and its application

technical field

The invention relates to the technical field of organic optoelectronic materials, and more particularly to an iridium metal complex and its application.

Background technique

Organic electroluminescence technology is the latest generation of flat-panel display technology, which can be used for flat-panel displays and lighting sources, and commercialized flat-panel displays have been put into the market. Electroluminescent devices have an all-solid-state structure, and organic electroluminescent materials are the core and foundation of the device. The development of new materials is the driving force behind the continuous progress of electroluminescent technology. In organic light-emitting, the phenomenon of phosphorescent luminescence has been admired by everyone since its discovery, because the luminous efficiency of phosphorescent materials is significantly higher than that of fluorescent materials, and theoretically it can reach 100% luminous efficiency, so many scientific research institutions are adding The research and development of large phosphorescent materials is trying to speed up the industrialization development through phosphorescent materials.

However, in the prior art, some phosphorescent materials are used in organic light-emitting devices with low efficiency and short lifetime. Therefore, how to provide an organic electroluminescent material with long life and high efficiency is an urgent problem for those skilled in the art.

SUMMARY OF THE INVENTION

In view of this, the present invention provides an iridium metal complex and its application. The iridium metal complex provided by the present invention can adjust the wavelength of the compound by selecting the ligand binding of a specific heterocyclic ring, and the obtained organometallic compound is used in After the organic electroluminescence device is used, the luminous efficiency of the device is increased, the lifespan is increased, and the starting voltage is decreased.

In order to achieve the above object, the present invention adopts the following technical solutions:

A kind of iridium metal complex, its structural formula is shown in chemical formula 1:

in,

Said R ₁ -R ₇ and Ar ₁ -Ar ₃ are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C ₁ -C ₈ alkyl, substituted or unsubstituted C ₆ -C ₁₀ Aryl, substituted or unsubstituted 4-8 membered aromatic heterocyclic group.

Preferably, the R ₁ -R ₇ include at least one fluorine substituent.

Preferably, the substitution position of R ₁ -R ₇ is any position in the ring;

The number of substituents of the R ₂ , R ₅ and R ₇ is 0-2;

The number of the R ₁ , R ₃ , R ₄ , and R ₆ substituents is 0-4.

Preferably, the number of R ₁ is 2, and it is an unsubstituted or 1-substituted C ₁ alkyl group or a C ₃ alkyl group;

The R ₂ is H;

The R ₃ is unsubstituted or 1 substituent substituted C ₃ alkyl;

The number of said R ₄ is 2-3, and it is fluorine, unsubstituted or 1 substituent substituted C ₁ alkyl and/or C ₃ alkyl;

The R ₅ is H or C ₃ alkyl;

The R ₆ number is 1-2, and is fluorine and/or C ₃ alkyl;

The _R7 is H.

Preferably, the alkyl group includes straight-chain alkyl, branched-chain alkyl, cycloalkyl, straight-chain alkyl substituted with at least one substituent, branched alkyl substituted with at least one substituent or at least one substituted One of the cycloalkyl substituted groups.

Preferably, the aromatic heterocyclic group is preferably an unsubstituted heteroaryl group or an aromatic heterocyclic group substituted with at least one substituent.

Preferably, the heteroatom in the heteroaryl group is nitrogen, sulfur or oxygen.

Preferably, the substituents are independently selected from one or more of halogen, deuterium or cyano.

Preferably, the iridium metal complex is selected from any one of the following structures:

The preparation method of described iridium metal complex, the steps are as follows:

1) Provide compound A, compound B and compound C represented by the following structural formulas:

2) fully react raw material A and raw material B with iridium trichloride to obtain bridging ligand intermediate C;

3) fully react the intermediate C and the intermediate D to obtain the iridium metal complex described in the chemical formula 1. As a further scheme of the present invention: the structure of the bridging ligand intermediate C is:

Its synthetic route is as follows:

Wherein: R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , Ar ₁ , Ar ₂ , Ar ₃ and the number of their respective substituents are consistent with the range defined in Chemical Formula 1.

An application of an iridium metal complex in an organic electroluminescence device, the organic electroluminescence device comprises the iridium metal complex, and further comprises a first electrode, a second electrode and a device disposed between the two electrodes. The organic layer between the two, wherein the organic layer contains the iridium metal complex shown in the chemical formula 1 of the present invention; the iridium metal complex shown in the chemical formula 1 of the present invention can exist in a single form or mixed with other substances in the organic layer middle.

Preferably, the organic layer includes a light-emitting layer, and the light-emitting layer contains the iridium metal complex represented by Chemical Formula 1 of the present invention. Preferably, the light-emitting layer of the organic electroluminescent device includes a host material and a dopant material, and the dopant material is an iridium metal complex represented by Chemical Formula 1 of the present invention.

Preferably, the mixing ratio of the host material of the light-emitting layer and the dopant material is 90:(10-99.5):0.5.

Preferably, the organic layer further includes a hole injection layer, a hole transport layer, a hole injection layer and a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, an electron injection layer, and both a hole injection layer and a hole transport layer. The electron transport also has one or more of the electron injection layers.

At least one functional layer contains the iridium metal complex represented by Chemical Formula 1 of the present invention.

Application of an organic electroluminescent device in organic light-emitting device, organic solar cell, electronic paper, organic photoreceptor or organic thin film transistor.

It can be seen from the above technical solutions that, compared with the prior art, the present disclosure provides an iridium metal complex, and the iridium metal complex of the novel structure provided by the present invention can be adjusted by selecting a specific heterocyclic ligand for binding. The wavelength of the compound, after the obtained organometallic compound is used in an organic electroluminescent device, improves the luminous efficiency and life of the device. In addition, the preparation method of the iridium metal complex provided by the present invention has simple preparation steps and high product purity.

Detailed ways

The following will clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1

A kind of iridium metal complex L006, namely the compound of numbering L006, concrete synthesis steps are as follows:

1) Under nitrogen protection system, weigh A-006 (28.36mmol, 8.55g) and B-006 (28.36mmol, 7.81g) IrCl ₃ ·3H ₂ O (28.36mmol, 10g) into the reaction system, add 500mL The mixed solution of ethylene glycol ether and 167 mL of pure water was refluxed at 120°C for 24 hours under nitrogen protection, and then cooled to room temperature, and a precipitate was precipitated. The precipitate was filtered under reduced pressure, washed with water, absolute ethanol, and petroleum ether in turn to obtain Bridging ligand C-006 as red powder (11.38 g, 50% yield);

2) Weigh intermediate C-006 (7.09mmol, 11.38g), add ligand D-006 (21.27mmol, 4.5g), then add ethylene glycol ether 300mL and potassium carbonate (7.5g) to the system, nitrogen Under protection, stirred at 120 ° C for 24 hours, filtered under reduced pressure, washed with alcohol, dried, used dichloromethane as a solvent, used silica gel column chromatography, the filtrate was concentrated and the solid was precipitated to obtain the final red compound L006 (4.16g, yield 30 %);

HPLC purity: greater than 99.5%;

Mass Spec: Calculated 978.29; Tested 978.30.

Elemental analysis: Calculated value C: 66.30%; H: 5.98%; F: 1.94%; Ir: 19.65%; N: 2.86; O: 3.27%; Test value: C: 66.30%; H: 6.00%; F: 1.95%; Ir: 19.66%; N: 2.86; O: 3.28%;

Specifically, the reaction formula of steps 1) to 2) is as follows:

In this embodiment, the iridium metal complex is used in the preparation of organic electroluminescent device products.

Example 2

A kind of iridium metal complex L015, namely the compound numbered L015, the specific synthesis steps are as follows: 1) under nitrogen protection system, weigh A-015 (28.36mmol, 8.55g) and B-015 (28.36mmol, 7.75g) ) IrCl ₃ ·3H ₂ O (28.36 mmol, 10 g) was added to the reaction system, a mixed solution of 500 mL of ethylene glycol ether and 167 mL of purified water was added, refluxed at 120° C. for 24 hours under nitrogen protection, and then cooled to room temperature, there was precipitation, The precipitate was filtered under reduced pressure, washed with water, anhydrous ethanol, and petroleum ether in turn and dried to obtain a red powder bridging ligand C-015 (11.84 g, yield 52%);

2) Weigh intermediate C-015 (7.4mmol, 11.84g), add ligand D-015 (22.2mmol, 5.65g), then add ethylene glycol ether 300mL and potassium carbonate (7.8g) to the system, nitrogen Under the protection, stirring at 120 ° C for 24 hours, filtering under reduced pressure, washing with alcohol, drying, using dichloromethane as solvent, using silica gel column chromatography, the filtrate was concentrated and the solid was precipitated to obtain the final red compound L015 (4.22 g, yield 28 %);

HPLC purity: greater than 99.5%;

Mass Spec: Calculated 1018.35; Tested 1018.30.

Elemental Analysis: Calculated C: 67.23%; H: 6.14%; F: 1.87%; Ir: 18.88%; N: 2.75; O: 3.14%; Tested: C: 67.20%; H: 6.15%; F: 1.88%; Ir: 18.90%; N: 2.75; O: 3.15%;

Specifically, the reaction formula of steps 1) to 2) is as follows:

In this embodiment, the iridium metal complex is used in the preparation of organic electroluminescent device products.

Example 3

A kind of iridium metal complex L023, namely the compound of numbering L023, concrete synthesis steps are as follows:

1) Under nitrogen protection system, weigh A-023 (28.36mmol, 7.84g) and B-006 (28.36mmol, 8.7g) IrCl ₃ ·3H ₂ O (28.36mmol, 10g) into the reaction system, add 500mL The mixed solution of ethylene glycol ether and 167 mL of pure water was refluxed at 120°C for 24 hours under nitrogen protection, and then cooled to room temperature, and a precipitate was precipitated. The precipitate was filtered under reduced pressure, washed with water, absolute ethanol, and petroleum ether in turn to obtain Bridging ligand C-023 as red powder (11.25 g, 49% yield);

2) Weigh intermediate C-023 (6.95mmol, 11.25g), add ligand D-023 (20.85mmol, 6.97g), add ethylene glycol ether 300mL and potassium carbonate (7.4g) to the system, nitrogen Under the protection, stirred at 120 ° C for 24 hours, filtered under reduced pressure, washed with alcohol, dried, used dichloromethane as solvent, used silica gel column chromatography, the filtrate was concentrated and the solid was precipitated to obtain the final red compound L023 (4.1 g, yield 27 %);

HPLC purity: greater than 99.5%;

Mass Spec: Calculated 1093.27; Tested 1093.30.

Elemental Analysis: Calculated C: 59.33%; H: 5.44%; F: 12.16%; Ir: 17.58%; N: 2.56; O: 2.93%; Tested: C: 59.30%; H: 5.45%; F: 12.15%; Ir: 17.60%; N: 2.856; O: 2.90%;

Specifically, the reaction formula of steps 1) to 2) is as follows:

In this embodiment, the iridium metal complex is used in the preparation of organic electroluminescent device products.

Example 4

A kind of iridium metal complex L035, namely the compound numbered L035, the specific synthesis steps are as follows: 1) under nitrogen protection system, weigh A-035 (28.36mmol, 8.55g) and B-035 (28.36mmol, 7.13g) ) IrCl ₃ ·3H ₂ O (28.36 mmol, 10 g) was added to the reaction system, a mixed solution of 500 mL of ethylene glycol ether and 167 mL of purified water was added, refluxed at 120° C. for 24 hours under nitrogen protection, and then cooled to room temperature, there was precipitation, The precipitate was filtered under reduced pressure, washed with water, anhydrous ethanol, and petroleum ether in turn and dried to obtain the bridged ligand C-035 (11.70 g, 53% yield) as a red powder;

2) Weigh intermediate C-035 (7.5mmol, 11.70g), add ligand D-035 (22.50mmol, 5.72g), then add ethylene glycol ether 300mL and potassium carbonate (8.0g) to the system, nitrogen Under the protection, stirred at 120 ° C for 24 hours, filtered under reduced pressure, washed with alcohol, dried, used dichloromethane as solvent, used silica gel column chromatography, the filtrate was concentrated and the solid was precipitated to obtain the final red compound L035 (4.05 g, yield 27.5 %);

HPLC purity: greater than 99.5%;

Mass spectrum: Calculated value is 982.25; Test value is 982.26.

Elemental Analysis: Calculated C: 64.81%; H: 5.64%; F: 3.87%; Ir: 19.57%; N: 2.85; O: 3.26%; Tested: C: 64.80%; H: 5.60%; F: 3.84%; Ir: 19.60%; N: 2.86; O: 3.25%;

Specifically, the reaction formula of steps 1) to 2) is as follows:

In this embodiment, the iridium metal complex is used in the preparation of organic electroluminescent device products.

In this embodiment, the iridium metal complex is used in the preparation of organic electroluminescent device products. The synthetic methods of other compounds are the same as above, and will not be repeated here. The mass spectra or molecular formulas of other synthetic examples are shown in the following table:

compound molecular formula MS calculated value Mass spectrometry test value L040 C₅₀H₄₈F₃IrN₂O₂ 958.16 958.15 L045 C₅₅H₄₅D₁₃FIrN₂O₂ 1003.38 1003.40 L051 C₅₆H₄₇D₁₃FIrN₂O₂ 1017.40 1017.35 L059 C₅₅H₅₇D₁₃F₄IrN₂O₂ 1046.28 1046.30 L066 C₅₆H₆₀FIrN₂O₂ 1004.32 1004.30 L072 C₅₂H₄₆F₇IrN₂O₂ 1056.16 1056.20 L079 C₅₄H₄₅D₁₃F₄IrN₂O₂ 1093.27 1093.30 L084 C₅₉H₅₃D₁₅FIrN₂O₂ 1063.51 1063.50 L088 C₅₅H₆₀FIrN₂O₂ 992.31 992.30 L099 C₆₀H₆₈FIrN₂O₂ 1060.43 1060.40 L105 C₄₆H₂₇D₁₃FIrN₂O₂ 877.13 877.10 L108 C₅₂H₃₉D₁₃FIrN₂O₂ 961.29 961.30 L111 C₅₈H₆₀D₆FIrN₂O₂ 1040.43 1040.40

The present invention also provides an organic electroluminescence device, wherein the organic electroluminescence device is made of the iridium metal complex, more specifically, the iridium metal complex shown in Chemical Formula 1.

Example 5

An organic electroluminescent device was prepared using the compound L006 prepared in Example 1, more specifically:

的ITO玻璃基板放在蒸馏水中清洗2次，超声波洗涤30分钟，用蒸馏水反复清洗2次，超声波洗涤10分钟，蒸馏水清洗结束后，异丙醇、丙酮、甲醇等溶剂按顺序超声波洗涤以后干燥，转移到等离子体清洗机里，将上述基板洗涤5分钟，送到蒸镀机里。首先ITO(阳极)上面蒸镀

紧接着蒸镀

主体物质化合物H1和掺杂物质化合物L00695:5重量比混合蒸镀

蒸镀电子传输层

蒸镀电子注入层

蒸镀阴极

形式制备得到有机电致发光器件。对得到的器件的性能发光特性测试，测量采用KEITHLEY2400型源测量单元，CS-2000分光辐射亮度计，以评价驱动电压，发光亮度，发光效率。The coating thickness is

The ITO glass substrate was washed twice in distilled water, ultrasonically washed for 30 minutes, repeatedly washed with distilled water for 2 times, and ultrasonically washed for 10 minutes. It was transferred to a plasma cleaner, the substrate was washed for 5 minutes, and then sent to a vapor deposition machine. First, ITO (anode) is evaporated on top

followed by evaporation

Host compound H1 and dopant compound L00695:5 weight ratio mixed vapor deposition

Evaporated Electron Transport Layer

Evaporated electron injection layer

Evaporated cathode

The organic electroluminescent device was prepared in the form of . To test the performance luminescence characteristics of the obtained device, KEITHLEY2400 source measurement unit and CS-2000 spectroradiometer were used to evaluate the driving voltage, luminous brightness and luminous efficiency.

Referring to the above method, compound L006 was replaced with L015, L023, L035, L040, L045, L051, L059, L066, L072, L079, L084, L088, L099, L105, L108, respectively, to prepare organic electroluminescent devices of corresponding compounds. .

Comparative Example 1

The organic electroluminescent device was prepared according to the same method as in Example 5, and the structure of the device structure compound was as follows:

The prepared organic electroluminescent device was tested in the same manner as in Example 5, and the results are shown in Table 1.

Table 1 Test results of organic electroluminescent devices in Example 5 and Comparative Example 1

As can be seen from Table 1, the organic electroluminescent device prepared by using the iridium metal complex provided by the present invention as the doping material for the light-emitting layer is similar to the organic electroluminescent device prepared by using the comparative compound Comparative Example 1 as the doping material for the light-emitting layer. ratio, the driving voltage is significantly reduced, and the current efficiency and life are significantly improved.

The various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments, and the same and similar parts between the various embodiments can be referred to each other.

The above description of the disclosed embodiments enables any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. an iridium metal complex, its structural formula is as shown in chemical formula 1:

in, Said R ₁ -R ₇ and Ar ₁ -Ar ₃ are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C ₁ -C ₈ alkyl, substituted or unsubstituted C ₆ -C ₁₀ Aryl, substituted or unsubstituted 4- to 8-membered aromatic heterocyclic groups. 2 . The iridium metal complex according to claim 1 , wherein the R ₁ to R ₇ at least comprise one fluorine substituent. 3 . 3. a kind of iridium metal complex according to claim 1, is characterized in that, described R ₁ -R ₇ substitution position is any position in the ring; The number of substituents of the R ₂ , R ₅ and R ₇ is 0-2; The number of the R ₁ , R ₃ , R ₄ , and R ₆ substituents is 0-4. 4. a kind of iridium metal complex according to claim 1, is characterized in that, described R ₁ quantity is 2, and is unsubstituted or 1 substituent substituted C ₁ alkyl or C ₃ alkyl; The R ₂ is H; The R ₃ is unsubstituted or 1 substituent substituted C ₃ alkyl; The number of said R ₄ is 2-3, and it is fluorine, unsubstituted or 1 substituent substituted C ₁ alkyl and/or C ₃ alkyl; The R ₅ is H or C ₃ alkyl; The R ₆ number is 1-2, and is fluorine and/or C ₃ alkyl; The _R7 is H. 5 . The iridium metal complex according to claim 1 , wherein the alkyl group comprises a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl group, and a straight-chain alkyl group substituted with at least one substituent. 6 . , branched alkyl substituted with at least one substituent or cycloalkyl substituted with at least one substituent. 6 . The iridium metal complex according to claim 1 , wherein the aromatic heterocyclic group is preferably an unsubstituted heteroaryl group or an aromatic heterocyclic group substituted with at least one substituent. 7 . 7 . The iridium metal complex according to claim 5 , wherein the heteroatom in the heteroaryl group is nitrogen, sulfur or oxygen. 8 . 8 . The iridium metal complex according to claim 6 , wherein the substituent is independently selected from one or more of halogen, deuterium or cyano. 9 . 9. an application of an iridium metal complex in an organic electroluminescent device, wherein the organic electroluminescent device comprises a light-emitting layer, and the light-emitting layer comprises the iridium described in any one of claims 1-7 metal complexes. 10. An application of the organic electroluminescent device according to claim 8 in organic light-emitting devices, organic solar cells, electronic paper, organic photoreceptors or organic thin film transistors.