Fluoro-iridium complexes, methods of making and using the same, and organic optoelectronic devices

Abstract

The application relates to the technical field of electronic materials, and discloses a fluorinated iridium complex, a preparation method and application thereof, and an organic photoelectric device. The fluorinated iridium complex has a structure shown in formula (I): R 1 is a C1-C13 alkyl substituent, R 2 is a C1-C13 alkyl substituent, and the substitution sites are the meta and para positions of a carbon atom of an isoquinoline phenyl linkage, X is an independently existing hydrogen atom, a fluorine atom or an alkyl substituent, wherein the alkyl substituent is a deuterated, partially deuterated or aryl-substituted alkyl group; the fluorinated iridium complex realizes high-efficiency supersaturation deep red light as a red phosphor material in an organic light-emitting device.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electronic materials, in particular to a fluorinated iridium complex, a preparation method and application thereof, and an organic optoelectronic device. BACKGROUND

[0002] Organic electroluminescence refers to a luminescence process in which organic materials convert electrical energy into light energy after being excited by current and electric field. According to the classification of core electroluminescent materials, traditional OLEDs can be divided into fluorescent OLEDs and phosphorescent OLEDs. Compared with fluorescent OLEDs, phosphorescent OLEDs have become the mainstream direction of OLED technology research and development due to their higher luminous efficiency.

[0003] Iridium (III) complexes are a kind of widely used phosphorescent materials. Although the above-mentioned organic luminescent materials have been commercialized in the manufacture of OLED panels and lighting appliances, there is still much room for improvement, such as reducing the material preparation process cost, improving the basic photoelectric performance of the material, improving the application experience quality of the final product, reducing the material matching cost in the device process, and improving the overall resistance and weather resistance of the material after device integration.

[0004] In the prior art, WO2015039723 discloses the synthesis of iridium complexes of polycyclic phenylpyridine and their application in organic optoelectronic devices; US20030072964 and US20070087321 disclose organic phosphorescent materials with phenylisoquinoline as ligand; US20080261076 discloses iridium heteroleptic complexes with 2-quinolinylphenyl and 2-isoquinolinylphenyl as ligands for use as organic phosphorescent materials; US20120181511 discloses the application of iridium complexes of 5-substituted phenylquinolines in light-emitting diodes, which involve a diketone structure The auxiliary ligand is phenylpyridine; CN107459535A discloses the synthesis of iridium complexes of 3, 4 or 5 monosubstituted phenylpyridines and their application in organic optoelectronic devices. The preparation method includes 3, 4-substituted, 3, 5-substituted, 4, 5-substituted and 3, 4, 5-substituted quinoline ligand coordination compounds, and the auxiliary ligand is a diketone structure. WO2013094620 discloses iridium heteroleptic complexes with polysubstituted pyrazine ligands for use as organic phosphorescent red materials; US20080261076 discloses organic light-emitting diode materials with phenylisoquinoline as ligand and pyridylimidazole and phenylpyridylimidazole as auxiliary ligand.

[0005] The demand of ultra-high definition display industry for color gamut of three primary colors is increasing, and it is necessary to develop organic light-emitting materials with high efficiency and super luminous saturation to realize wider color gamut without filtering. According to the colorimetric coordinates of the International Commission on Illumination (CIE), a monochromatic light with a wavelength less than 610 nm can obtain a red light with high saturation. Considering that the spectrum of organic light-emitting display has a certain wavelength range, an organic light-emitting diode with a light-emitting peak between 620-630 nm can obtain a red light with a color gamut of 100%, i.e. CIE coordinates (x=0.67, y=0.33). According to the International Telecommunication Union (ITU) 2020 color standard, the CIE coordinates of the red light material of the higher display standard need to be (x>0.70, y<0.29). According to the characteristics of the wide spectrum of organic light-emitting, the device requires a light-emitting wavelength less than 636 nm, which can meet the display requirements of high resolution. If the light-emitting spectrum is narrowed, the same chromaticity can be obtained in a shorter wavelength range. In the short wavelength red light region, the visual perception is high, so the narrow spectrum red light can greatly improve the luminous brightness and luminous efficiency, and therefore has an irreplaceable advantage in high-definition and VR display. It is also the main direction of high-quality development in the future display and special red light emitting field. SUMMARY

[0006] The purpose of the present application is to overcome the deficiency of the prior art that the OLED device lacks complex luminescent materials capable of emitting stable and efficient red light, and to provide a fluorinated iridium complex, a preparation method and application thereof, and an organic optoelectronic device. The fluorinated iridium complex as a red phosphor material realizes high-efficiency super-saturated deep red light in an organic light-emitting device.

[0007] To achieve the above-mentioned purpose, the first aspect of the present application provides a fluorinated iridium complex, wherein the fluorinated iridium complex has a structure shown in formula (I):

[0008]

[0009] wherein, part is a phenyl-substituted isoquinoline main ligand;

[0010] wherein, part is a 1,3 dicarbonyl auxiliary ligand;

[0011] wherein, R 1 is a C1-C13 alkyl substituent, R 2 is a C1-C13 alkyl substituent, the substitution site is meta and para of the isoquinoline phenyl linking carbon atom, and X is an independently existing hydrogen atom, a fluorine atom or an alkyl substituent, wherein the alkyl substituent is deuterated, partially deuterated or aryl-substituted alkyl.

[0012] The second aspect of the present application provides a preparation method of the aforementioned fluorinated iridium complex, wherein the preparation method comprises:

[0013] (1) performing a first reaction on a main ligand and a salt containing a trivalent iridium ion in the presence of a protective gas and a first reagent to obtain a dimer represented by formula (II);

[0014] (2) performing a second reaction on the dimer represented by formula (II) and an auxiliary ligand in the presence of a protective gas, sodium carbonate and a second reagent to obtain the fluorinated iridium complex represented by formula (I);

[0015]

[0016] wherein the definitions of the groups in formula (I) and formula (II) are the same as the aforementioned definitions.

[0017] The third aspect of the present application provides an application of the aforementioned fluorinated iridium complex in a light-emitting device, a biomarker or in an imaging technology.

[0018] The fourth aspect of the present application provides an organic photoelectric device, wherein the organic photoelectric device comprises a light-emitting layer, and the light-emitting layer contains the aforementioned fluorinated iridium complex.

[0019] Through the above technical solution, the present application modifies the main ligand of the organometallic complex of the ring metal iridium by a freely rotating phenyl group, constructs a ligand donor fragment by a fluorinated dimethylphenyl group, controls the energy gap within the deep red light-emitting range, achieves the purpose of narrowing the light-emitting spectrum while maintaining a very high quantum conversion efficiency, and proves by a device that the material can exhibit the characteristics of super-saturated red light in the device, and has high efficiency and good stability. According to the spectral characteristics, electrochemical properties and compound modification functions of these molecules, it can be determined that the fluorinated iridium complex can be used to prepare high-quality super-saturated red light OLED related devices and application appliances. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 NMR spectrum for structural characterization of iridium complex 7;

[0021] Figure 2 NMR spectrum for structural characterization of iridium complex 31;

[0022] Figure 3 Mass spectrum of iridium complex 7;

[0023] Figure 4 Mass spectrum of iridium complex 31;

[0024] Figure 5 Luminescence spectrum of iridium complex 7;

[0025] Figure 6 luminescence spectrum of iridium complex 31;

[0026] Figure 7 absorption spectrum of iridium complex 7;

[0027] Figure 8 OLED structure using iridium complex 7 as electroluminescent material according to the present application;

[0028] Figure 9 Comparison of photoluminescence spectra of complex 7 and iridium complex 37;

[0029] Figure 10 Electroluminescence spectra and CIE coordinates of devices using complex 7 and 37 as red dopant materials after the devices are prepared into OLEDs;

[0030] Figure 11 Luminescence (J-V) of OLED devices using iridium complex 7 and 37 as red dopant materials after the devices are prepared into OLEDs at room temperature;

[0031] Figure 12 Voltage-luminance (V-L) of OLED devices using iridium complex 7 and 37 as red dopant materials after the devices are prepared into OLEDs at room temperature;

[0032] Figure 13 External quantum efficiency of OLED devices using iridium complex 7 and 37 as red dopant materials after the devices are prepared into OLEDs at room temperature;

[0033] Figure 14 Photoluminescence decay curves of complex 7 and 37 as red dopant materials after the devices are prepared into OLEDs;

[0034] Figure 15 Electroluminescence decay curves of devices prepared from complex 7 and 37. DETAILED DESCRIPTION

[0035] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as exactly that endpoint. Any values that fall within common

[0036] As previously described, the first aspect of the present application provides a fluorinated iridium complex, wherein the fluorinated iridium complex has a structure shown in formula (I):

[0037]

[0038] wherein, partially phenyl-substituted isoquinoline main ligand;

[0039] wherein, partially 1,3-dicarbonyl auxiliary ligand;

[0040] wherein, R 1 is a C1-C13 alkyl substituent, R 2 is a C1-C13 alkyl substituent, the substitution sites are the meta and para positions of the isoquinoline phenyl bond carbon atom, and X is an independently existing hydrogen atom, fluorine atom, or alkyl substituent, wherein the alkyl substituent is deuterated, partially deuterated, or aryl-substituted alkyl.

[0041] The inventors of the present application unexpectedly found that the introduction of a freely rotating phenyl group at a specific site in the main ligand reduces the luminescence energy gap, red shifts the intrinsic luminescence wavelength of the compound to the deep red light region, and the time electroluminescent device emits light with a wavelength of 635 nm or more, CIE coordinates (x≥0.70, Y≤0.29), which better meets the color standard of the International Telecommunication Union (ITU) 2020 high-saturation red light. At the same time, the complex at least maintains the original high-efficiency photoelectric conversion characteristics and the stability of light, electricity, and heat of the original complex (isoquinoline 4-unsubstituted), so that it can be used as a doped luminescent material for electroluminescent device-related appliances, and can have excellent appliance service life. According to the spectral characteristics and compound modification functions of these molecules, it is clear that such molecules can be used to prepare high-quality super-saturation red light organic electroluminescent related devices and application appliances.

[0042] According to the present application, partially phenyl-substituted isoquinoline ligand, which is also a main ligand (main ligand), refers to a part that mainly produces an electronic energy level transition leading to luminescence; 1,3-dicarbonyl auxiliary ligand, which is an auxiliary ligand (auxiliary ligand) part; Ir 3+ refers to a trivalent central coordination iridium metal ion, which is an octahedral structure; the ligand is bidentate and is monovalent.

[0043] According to a preferred specific embodiment of the present application, in formula (I):

[0044] The alkyl group is a straight-chain or branched-chain alkyl group; preferably a C1-C6 alkyl group; more preferably, the alkyl group includes but is not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,3-dimethylpropyl, and 1-ethylpropyl, cyclopentyl, cyclohexyl, 2-methyl-3-pentyl, or 3,3-dimethyl-2-butyl.

[0045] The hydrogen atom is not isotopically distinguished, including protium, deuterium, tritium or natural state hydrogen;

[0046] According to a preferred embodiment of the present application, in formula (I):

[0047] X is a deuterated molecule, R 1 and R 2 is selected from deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated n-pentyl, deuterated 1-methylbutyl, deuterated 2-methylbutyl, deuterated 3-methylbutyl, deuterated 1,2-dimethylpropyl, deuterated 2,3-dimethylpropyl, deuterated 1-ethylpropyl, deuterated cyclopentyl, deuterated cyclohexyl, deuterated 2-methyl-3-pentyl, etc., X is an independently existing hydrogen atom, fluorine atom or alkyl substituent, and the alkyl substituent can be deuterated, partially deuterated or aryl-substituted alkyl.

[0048] According to a preferred embodiment of the present application, in formula (I):

[0049] The fluorinated iridium complex is selected from at least one of the following:

[0050]

[0051]

[0052]

[0053] According to a preferred embodiment of the present application, the main ligand of the organometallic complex compound R 1 and X are most likely to be the following common structures:

[0054]

[0055] According to a preferred embodiment of the present application, the auxiliary ligand of the organometallic complex compound R 2 are most likely to be the following common structures:

[0056]

[0057] According to a more preferred embodiment of the present application, the fluorinated iridium complex is selected from at least one of the following:

[0058]

[0059] According to a particularly preferred embodiment of the present application, the fluorinated iridium complex is selected from:

[0060]

[0061] The present application is not particularly limited to the method for preparing the fluorinated iridium complex, and those skilled in the art can obtain the appropriate steps for synthesizing the fluorinated iridium complex according to the structural formula provided by the present application, combined with the known synthesis method in the field of organic synthesis. The preparation methods of several specific compounds are exemplarily provided in the following of the present application, and those skilled in the art should not be construed as a limitation of the present application.

[0062] However, in order to make the yield and purity of the red phosphor fluorinated iridium complex of the present application higher, as described above, the present application provides a preparation method of the aforementioned fluorinated iridium complex, wherein the preparation method comprises:

[0063] (1) a first reaction of the main ligand and the salt containing trivalent iridium ion in the presence of a protective gas and a first reagent to obtain a dimer represented by formula (II);

[0064] (2) a second reaction of the dimer represented by formula (II) and the auxiliary ligand in the presence of a protective gas, sodium carbonate and a second reagent to obtain the fluorinated iridium complex represented by formula (I);

[0065]

[0066]

[0067] wherein the definitions of the groups in formula (I) and formula (II) are the same as the aforementioned definitions.

[0068] According to the present application, the salt containing trivalent iridium ion is iridium trichloride trihydrate and / or iridium trichloride with multiple crystal water.

[0069] According to the present application, the first reagent is ethylene glycol ethyl ether and / or water.

[0070] According to the present application, the second reagent is ethylene glycol ethyl ether.

[0071] According to the present application, the molar ratio of the amount of use of the main ligand, the salt containing trivalent iridium ion, the first reagent is (4-6):1:(20-50), preferably 5:1:20.

[0072] According to the present application, the molar ratio of the amount of use of the dimer, the auxiliary ligand, sodium carbonate, the second reagent is 1:(2-10):(5-20):(100-300), preferably 1:2:5:100.

[0073] According to the present application, the first reaction is carried out at a temperature of 100-150°C for 12-20 hours, and the second reaction is carried out at a temperature of 110-200°C for 12-30 hours.

[0074] According to a particularly preferred embodiment of the present application, the preparation method of the fluorinated iridium complex comprises at least the following two steps: a precursor is reacted with trivalent iridium to obtain a dimer; and the dimer is reacted with a ligand precursor compound through a two-step reaction to obtain the compound of the general formula I. The chemical reaction equation is as follows:

[0075]

[0076] The third aspect of the present application provides an application of the fluorinated iridium complex in a light-emitting device, a biomarker or an imaging technology.

[0077] According to the present application, preferably, the fluorinated iridium complex is applied in a light-emitting device.

[0078] In the present application, the light-emitting device can be specifically used in an organic electronic component, which is an organic light-emitting diode, a light-emitting diode, a compact fluorescent lamp, an incandescent lamp, an organic photovoltaic cell, an organic field effect transistor or a light-emitting electrochemical cell.

[0079] The fourth aspect of the present application provides an organic optoelectronic device, wherein the organic optoelectronic device comprises a light-emitting layer, and the light-emitting layer comprises the fluorinated iridium complex.

[0080] According to the present application, the fluorinated iridium complex is a light-emitting material, a host material, a guest material or other auxiliary functional material in the light-emitting layer.

[0081] The present application will be described in detail below through examples.

[0082] Example 1

[0083] This example is to illustrate the synthesis and structural characterization of the deuterated iridium complex 7.

[0084]

[0085] Synthesis of the dimer A: 75 ml of a sealed tube was added with 1-(4-fluoro-3,5-dimethylphenyl)-6-(p-tolyl)isoquinoline (4.7 mmol), iridium trichloride trihydrate (0.9 mmol), ethylene glycol ethyl ether (15 mL) and water (5 mL), and the reaction bottle was replaced with nitrogen atmosphere. The reaction system was heated to 100°C and stirred for 12 hours. The reaction liquid was cooled to room temperature, and solid was precipitated, washed with water and ethyl ether, and dried to obtain the dimer A (76%).

[0086] Synthesis of iridium complex 7: To a 15 ml sealed tube was added dimer A (0.05 mmol), 3,7-diethyl nonane-4,6-dione (0.1 ml), sodium carbonate (0.25 mmol) and ethylene glycol ethyl ether (3 mL), nitrogen was bubbled for three minutes, the reaction system was heated to reflux for 12 hours. The reaction solution was cooled to room temperature, filtered, the filtrate was rotary evaporated and column chromatography (petroleum ether: ethyl acetate = 10: 1) to give iridium complex 7 (69%). NMR (400 MHz, CDC13) δ 8.96 (d, J = 9.2 Hz, 2H), 8.15 (d, J = 6.8 Hz, 2H), 8.03 (d, J = 7.2 Hz, 2H), 7.98 (d, J = 1.6 Hz, 2H), 7.95-7.92 (m, 2H), 7.69 (d, J = 8.0 Hz, 4H), 7.35 (d, J = 8.0 Hz, 4H), 7.21 (d, J = 6.4 Hz, 2H), 4.84 (s, 1H), 2.45 (s, 6H), 2.31 (s, 3H), 2.30 (s, 3H), 1.60-1.54 (m, 2H), 1.40 (s, 3H), 1.39 (s, 3H), 1.33-1.25 (m, 2H), 1.15-1.08 (m, 2H), 0.94-0.85 (m, 4H), 0.44 (t, J = 7.6 Hz, 6H), -0.14 (t, J = 7.2 Hz, 6H).

[0087] MS (ESI): 1084.6 [M] + Emission peak in DCM at 609nm, FWHM = 48nm, peak in PMMA at 608nm, FWHM = 49nm.

[0088] In addition, Figure 1 The nuclear magnetic hydrogen spectrum for structural characterization of iridium complex 7, which can be explained by the hydrogen spectrum that the deuterium iridium complex 7 can exist independently and can be separated, purified and characterized.

[0089] Figure 3 The mass spectrum of iridium complex 7, the mass spectrum of the molecule shows that the molecular signal shows that the M / C peak is 1084.6, which is consistent with the molecular ion peak of compound 7, which shows that the structure of the complex is the designed structure.

[0090] Figure 5 The luminescence spectrum of iridium complex 7, from Figure 5 It can be seen that the emission peaks in the solution and the thin film are almost at the same position, there is no large shift, and the half peak width of the spectrum is relatively narrow, and the main region of the luminescence is in the red light region.

[0091] Figure 7The absorption spectrum of iridium complex 7 is shown in Figure 1. Figure 7 It can be seen that strong absorption is shown in solution and thin film, which indicates that the material is a good luminescent material.

[0092] Figure 8 The OLED structure using iridium complex 7 as an electroluminescent material is shown in Figure 2, which shows the structure of the device, including the light-emitting layer, electron / hole transport layer, electron / hole injection layer and anode and cathode.

[0093] Example 2

[0094] This example is directed to the synthesis and structural characterization of deuterated iridium complex 13.

[0095]

[0096] Synthesis of dimer B: Into a 75 ml sealed tube was added 1-(4-fluoro-3,5-dimethylphenyl)-6-(3-methylphenyl)isoquinoline (4.7 mmol), iridium trichloride trihydrate (0.9 mmol), ethylene glycol ethyl ether (15 mL) and water (5 mL), and the reaction vessel was purged with nitrogen. The reaction system was heated to 100°C and stirred for 12 hours. The reaction solution was cooled to room temperature, and solid was precipitated, washed with water and ethyl ether, and dried to obtain dimer B (76%).

[0097] Synthesis of iridium complex 13: Into a 15 ml sealed tube was added dimer B (0.05 mmol), 3,7-diethyl nonane-4,6-dione (0.1 ml), sodium carbonate (0.25 mmol) and ethylene glycol ethyl ether (3 mL), and the reaction vessel was purged with nitrogen for three minutes. The reaction system was heated to reflux for 12 hours. The reaction solution was cooled to room temperature, filtered, and the filtrate was rotary evaporated and column chromatographed (petroleum ether: ethyl acetate = 10:1) to obtain iridium complex 13 (69%).

[0098] In addition, Figure 2 The 1H NMR spectrum for structural characterization of iridium complex 31 is shown in Figure 4. The hydrogen spectrum shows that the complex can exist independently and stably, and can be separated, purified and characterized.

[0099] Figure 4 The mass spectrum detection chart of iridium complex 31 is shown in Figure 5. The molecular signal of the mass spectrum shows that the M / C peak value is 1092.6, which is consistent with the molecular ion peak of iridium complex 31, indicating that the structure of the complex is the designed structure.

[0100] Figure 6 The luminescence spectrum of iridium complex 31 is shown in Figure 6. Figure 6 It can be seen that the emission peak of the spectrum is located in the range of 613-615 nm, and the half peak width is about 50 nm, which belongs to a relatively narrow half peak width, and the main luminescence region is still in the red light region.

[0101] Example 3

[0102] This example is directed to the synthesis and structural characterization of deuterated iridium complex 25.

[0103]

[0104] Synthesis of dimer C: To a 75 ml sealed tube was added 1-(4-fluoro-3,5- dimethylphenyl)-6-(4-fluorophenyl)isoquinoline (4.7 mmol), iridium trichloride trihydrate (0.9 mmol), ethylene glycol ethyl ether (15 mL) and water (5 mL), and the reaction vessel was purged with nitrogen. The reaction was heated to 100 °C and stirred for 12 h. The reaction was cooled to room temperature and a solid precipitated. The solid was washed with water and dried to give dimer C (76%).

[0105] Synthesis of iridium complex 25: To a 15 ml sealed tube was added dimer C (0.05 mmol), 3,7-diethylnonane-4,6-dione (0.1 mL), sodium carbonate (0.25 mmol) and ethylene glycol ethyl ether (3 mL), and the reaction vessel was purged with nitrogen for three minutes. The reaction was heated to reflux for 12 h. The reaction was cooled to room temperature and filtered. The filtrate was evaporated and purified by column chromatography (petroleum ether: ethyl acetate = 10: 1) to give iridium complex 25 (69%).

[0106] Example 4

[0107] This example is directed to the synthesis and structural characterization of deuterated iridium complex 31.

[0108]

[0109] Synthesis of dimer D: To a 75 ml sealed tube was added 1-(4-fluoro-3,5- dimethylphenyl)-6-(3-fluorophenyl)isoquinoline (4.7 mmol), iridium trichloride trihydrate (0.9 mmol), ethylene glycol ethyl ether (15 mL) and water (5 mL), and the reaction vessel was purged with nitrogen. The reaction was heated to 100 °C and stirred for 12 h. The reaction was cooled to room temperature and a solid precipitated. The solid was washed with water and dried to give dimer D (76%).

[0110] Synthesis of iridium complex 31 : To a 15 ml sealed tube was added dimer D (0.05 mmol), 3,7-diethyl nonane-4,6-dione (0.1 ml), sodium carbonate (0.25 mmol) and ethylene glycol ethyl ether (3 mL), and the reaction vessel was bubbled with nitrogen for three minutes. The reaction was heated to reflux for 12 hours. The reaction was cooled to room temperature, filtered, and the filtrate was evaporated to dryness and purified by column chromatography (petroleum ether: ethyl acetate = 10: 1) to give iridium complex 31 (69%). NMR (400 MHz, CDC13) δ 9.00 (d, J = 8.8 Hz, 2H), 8.18 (d, J = 6.4 Hz, 2H), 8.03 (d, J = 7.6 Hz, 2H), 7.99 (d, J = 2.0 Hz, 2H), 7.93-7.91 (m, 2H), 7.58-7.56 (m, 2H), 7.54-7.47 (m, 4H), 7.23 (d, J = 6.4 Hz, 2H), 7.18-7.13 (m, 2H), 4.85 (s, 1H), 2.32 (s, 3H), 2.31 (s, 3H), 1.60-1.57 (m, 2H), 1.41 (s, 3H), 1.40 (s, 3H), 1.32-1.28 (m, 2H), 1.16-1.11 (m, 2H), 0.91-0.90 (m, 4H), 0.45 (t, J = 7.6 Hz, 6H), -0.14 (t, J = 7.2 Hz, 6H).

[0111] MS (ESI): 1092.6 [M] + Emission peak in DCM at 615 nm, FWHM = 50 nm, peak in PMMA at 613 nm, FWHM = 48 nm.

[0112] Comparative Example 1

[0113] This comparative example is directed to the preparation of complex 37.

[0114]

[0115] Detailed Preparation Method:

[0116] Synthesis of dimer E: To a 75 ml sealed tube was added 1-(4-fluoro-3,5- dimethylphenyl)isoquinoline (4 mmol), iridium trichloride trihydrate (0.8 mmol), ethylene glycol ethyl ether (14 mL) and water (4 mL), and the reaction vessel was bubbled with nitrogen. The reaction was heated to 100 °C and stirred for 12 hours. The reaction was cooled to room temperature, and a solid precipitated. The solid was washed with water and ethyl ether, and dried to give dimer E.

[0117] Synthesis of iridium complex 37: Into a 15 ml sealed tube was added dimer E (0.05 mmol), 3,7-diethyl nonane-4,6-dione (0.1 ml), sodium carbonate (0.25 mmol) and ethylene glycol ethyl ether (3 mL), nitrogen was bubbled for three minutes, the reaction system was heated to reflux for 12 hours. The reaction solution was cooled to room temperature, filtered, the filtrate was rotary evaporated and column chromatography (petroleum ether: ethyl acetate = 10:1) to give iridium complex 37.

[0118] Test Example 1

[0119] Characterization test of iridium complex material.

[0120] The optical properties of the deuterated iridium complexes described in the present application were compared, and the results are shown in Table 1.

[0121] The test method is as follows: The band gap value (Eg) and LUMO value of the material are measured by cyclic voltammetry. The whole test process is carried out on a CHI600D electrochemical workstation (Shanghai Chenhua Instrument Co., Ltd.) in a glove box (Lab2000, Etelux), with a Pt column as the working electrode, Ag / AgCl as the reference electrode, and a Pt wire as the auxiliary electrode to form a three-electrode system. The medium used in the test process is 0.1M tetrabutylammonium hexafluorophosphate dimethylamide solution, and the measured potential is taken as the internal standard with the addition of ferrocene (Fc). The HOMO value of the material is directly tested by Model IPS-4 Ionization Energy Measurement System. The fluorescence quantum efficiency of the material is calculated according to the formula (wherein: Φ s is the fluorescence quantum yield of the sample, Φ r is the fluorescence quantum yield of the standard, η is the refractive index of the solution, A s and A r are the absorption values of the sample and the standard at the fluorescence excitation wavelength, I s and I r are the fluorescence integral areas of the sample and the standard) using a relative method. The material and the standard with known quantum yield are configured into the same concentration of polymethyl methacrylate (PMMA) trichloromethane solution, and are spin-coated into a film. Under the same measurement conditions, the ultraviolet absorption spectrum (GENESYS 10S, Thermo) and the fluorescence spectrum (F97pro fluorescence spectrophotometer, Prism Technology) are measured. The photon energy (ET1) of the material is calculated from the formula E = hν = 1240 / λ (where λ is the tangent wavelength of the starting position of the fluorescence spectrum of the material PMMA film).

[0122] Table 1

[0123]

[0124] Note:a The energy of triplet state was measured by cyclic voltammetry b The energy of triplet state was measured by cyclic voltammetry c 5wt% concentration in PMMA.

[0125] Test Example 2

[0126] The iridium complex 7 was doped into the host material as a light-emitting material to prepare device OLED, and the OLED device structure is shown in Figure 8 The cathode is a cathode, the EIL is an electron injection layer, the ETL is an electron transport layer, the HTL is a hole transport layer, the HIL is a hole injection layer, and the ITO is an indium oxide electrode. The iridium complex 7 is included in the EML (light-emitting layer) as an electroluminescent material, and the light-emitting layer includes a host material and a light-emitting material. The iridium complex 7 was applied to the device, and the luminescent performance and other parameters were compared.

[0127] Figure 9 The photoluminescence spectra of complexes 7 and 37 are shown in the following figure, from Figure 9 It can be seen that: compared with 7, the emission peak of complex 37 is blue-shifted by nearly 10 nm. The addition of an aryl group at the 4-substituted position of isoquinoline is beneficial to the red shift of the emission spectrum, but it does not change the half-width of the spectrum much.

[0128] Figure 10 The electroluminescence spectra and device electroluminescence CIE coordinate diagrams of complexes 7 and 37 used as red light doping materials to prepare OLED devices are shown in the following figure, from Figure 10 The OLED prepared from complex 37 has a good electroluminescence spectrum, and the spectral wavelength is 605 nm, which is red-shifted from the peak in PMMA. The device prepared from complex 7 has a spectral wavelength of 621 nm, as shown in Figure 10 The EL peak of device 37 is 605 nm, and the CIE is (0.646, 0.353). The EL peak of complex 7 is 621 nm, and the CIE is (0.670, 0.328), which is very close to the standard red light (0.708, 0.292) of B.T.2020. The maximum display saturation based on complex 37 is 94.7%, and the maximum display saturation that can be achieved by complex 7 is 100.0%. This shows that complex 7 has better performance.

[0129] Figure 11 and Figure 12 The light-emitting diagram (J-V) and the voltage-luminance change diagram (V-L) of the OLED device prepared by using iridium complexes 7 and 37 as red light doping materials at room temperature are shown in the following figure. The current-voltage curve and the voltage-luminance curve show that the starting voltage of the device corresponding to the complex is below 3V, indicating that the core light-emitting material has very good light-emitting performance and stability during the light-emitting process.

[0130] Figure 13The luminescence external quantum efficiency diagram of the OLED device prepared by using the iridium complexes 7 and 37 as red light doping materials at room temperature is shown in the figure, and it can be seen from the figure that the complex 7 has a higher electroluminescent efficiency of 24%, which indicates that the material is more suitable for preparing high-efficiency light-emitting devices than 7.

[0131] Figure 14 The photoluminescence decay curve of the device prepared by using the complexes 7 and 37 as red light doping materials over time is shown in the figure. The decay test is carried out by irradiating the stable polystyrene polymer film doped with 5% iridium complex with 50 mW / m 2 of ultraviolet light, and the intensity of photoluminescence is recorded, and finally the function relationship between the luminescence decay of the compound and time is obtained. Figure 14 It is shown that the luminescence intensity of the complex 7 is maintained well, the photoluminescence decay is slow, and the complex 7 has better optical stability.

[0132] Figure 15 The electroluminescence decay curve of the device prepared by using the complexes 7 and 37 over time is shown in the figure, and the device structure is as follows:

[0133] ITO / HT21:H09(100,5%) / HT21(300) / HT18(100) / PH323:RD(200,2%) / ET14(400) / ET20(100) / ET20:IN05(100,1%) / Al(1500), wherein RD represents the complexes 7 and 37. The starting current density of the electroluminescence decay test is 50 mA / cm 2 . Figure 15 It is shown that the two complexes have good stability, and the complex 7 has better performance.

[0134] Test Example 3

[0135] The iridium complexes are prepared into devices, and the related data of the devices are tested, and the data comparison test results are shown in Table 2.

[0136] Table 2

[0137]

[0138] As shown in Table 2, it can be seen from the device data comparison that the electroluminescence wavelength of the device is mainly determined by the photoluminescence of the iridium complex itself, and under the same conditions, the efficiency of the device is also consistent with the PLQE trend of the iridium complex itself. Therefore, the high-PLQE iridium complex compound disclosed in the present application can obtain high device efficiency in other devices.

[0139] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including that each technical feature is combined in any other suitable manner. These simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A fluoro-iridium complex characterized in that, The fluorinated iridium complex is selected from at least one of the following:

2. The fluoroiridium complex of claim 1, wherein, The fluorinated iridium complex is selected from at least one of the following:

3. A process for the preparation of a fluoro-iridium complex according to claim 1 or 2, characterized in that The preparation method comprises: (1) in the presence of a protective gas and a first solvent, a main ligand and a salt containing a trivalent iridium ion are subjected to a first reaction to obtain a dimer represented by formula (II); (2) in the presence of a protective gas, sodium carbonate and a second solvent, the dimer represented by formula (II) and an auxiliary ligand are subjected to a second reaction to obtain the fluorinated iridium complex represented by formula (I); wherein the definitions of the groups in formula (I) and formula (II) are such that the fluorinated iridium complex prepared is the fluorinated iridium complex of claim 1 or 2.

4. The production method according to claim 3, wherein The salt containing a trivalent iridium ion is iridium trichloride trihydrate and / or iridium trichloride with multiple crystal waters; And / or, the first solvent is ethylene glycol ethyl ether and / or water; And / or, the second solvent is ethylene glycol ethyl ether; And / or, the molar ratio of the use amount of the main ligand, the salt containing a trivalent iridium ion, the first solvent is (4-6):1:(20-50); And / or, the molar ratio of the use amount of the dimer, the auxiliary ligand, sodium carbonate, the second solvent is 1:(2-10):(5-20):(100-300).

5. The production method according to claim 3, wherein The conditions of the first reaction include: temperature is 100-150℃, time is 12-20h; And / or, the conditions of the second reaction include: temperature is 110-200℃, time is 12-30h.

6. Use of the fluorinated iridium complex of claim 1 or 2 in a light-emitting device, a biological marker or in an imaging technology.

7. An organic optoelectronic device, characterized in that The organic photoelectric device comprises a light-emitting layer, and the light-emitting layer comprises the fluorinated iridium complex of claim 1 or 2.

8. The organic photovoltaic device of claim 7, wherein, The fluorinated iridium complex is one or more of a light-emitting material, a host material and a guest material in the light-emitting layer.

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