CN110229192B

CN110229192B - Deuterated iridium complex and preparation method and application thereof

Info

Publication number: CN110229192B
Application number: CN201910548621.6A
Authority: CN
Inventors: 杭晓春; 王英; 徐丹丹
Original assignee: Nanjing Jianuolin Photoelectric Technology Co ltd
Current assignee: Nanjing Jianuolin Photoelectric Technology Co ltd
Priority date: 2019-06-24
Filing date: 2019-06-24
Publication date: 2023-04-18
Anticipated expiration: 2039-06-24
Also published as: CN110229192A

Abstract

The invention discloses a deuterated iridium complex, a preparation method thereof, application of the compound in an electroluminescent material and related photoelectric physical properties. Through modification of an organic ligand of the cyclometalated iridium (III) complex, the fluorescence quantum efficiency (PLQE) of luminescent material molecules can be improved, the stability of the complex in the luminescent process is improved, and the application stability of a material device can be further improved. According to the spectral characteristics, electrochemical properties and compound modification functions of the molecules, the molecules can be clearly used for preparing high-quality OLED related devices and application appliances.

Description

Deuterated iridium complex and preparation method and application thereof

Technical Field

The invention belongs to the technical field of electronic materials, and particularly relates to a deuterated iridium complex, a preparation method thereof, and application of the complex in an electroluminescent device.

Background

Organic electroluminescence refers to a light emitting process in which an organic material converts electric energy into light energy after being excited by current and electric field, and the electroluminescence phenomenon was originally discovered in the professor Pope of New York university in 1963. Organic light emitting materials can be closer to the requirements in terms of adaptability to light than inorganic light emitting materials. Displays and light emitters made based on Organic Light Emitting Diode (OLED) technology have a flexible profile and add a number of artistic elements to the electronic devices. The earliest Organic electroluminescent devices were developed by Eastman Kodak by using small Organic molecules of aromatic amines as hole transport layers and 8-hydroxyquinoline aluminum as the light emitting layer ("Organic electroluminescent diodes" Tang, vanslyke et al, applys Lett, vol. 51, pp. 913-915, 1987). Such devices using organic molecules as core light-emitting materials are called organic light-emitting diodes (OLEDs), which can be applied in new display and lighting fields, and have many advantages and potentials. The luminescent device prepared by the organic material has the advantages of high quantum efficiency, high brightness, high luminous efficiency and the like; the light-emitting device made of the organic light-emitting material has the advantages of light weight, thinness, flexibility and the like in appearance, and particularly, the light-emitting device made of the organic light-emitting material has the advantage that other light-emitting materials cannot be compared with the light-emitting device. The conventional OLEDs can be classified into fluorescent type OLEDs and phosphorescent type OLEDs according to the classification of the electroluminescent material of the core. Compared with fluorescent OLEDs (theoretical luminous efficiency is 25% at the highest), phosphorescent OLEDs (theoretical luminous efficiency 100%) are the mainstream direction for OLED technology research and development due to their higher luminous efficiency. ("high effective phosphor emission from organic electroluminescent device devices" M.A.Baldo, D.F.O' Brien, Y.you, A.Shoustikov, S.Sibley, M.E.Thompson & S.R.Forrest Nature Vol 3951998-154)

The decay of excitons from the singlet excited state to the ground state produces rapid luminescence, i.e., fluorescence. The decay of excitons from the triplet excited state to the ground state generates light, i.e., phosphorescence. Phosphorescent metal complexes, such as platinum complexes, have shown their potential to harvest both singlet and triplet excited states and to achieve 100% internal quantum efficiency, since the strong spin-orbit coupling (ISC) of heavy metal atoms is very effective in enhancing the electron spin state cross-change between singlet and triplet excited states. Therefore, phosphorescent metal complexes are good candidates as dopants in the light emitting layer of Organic Light Emitting Devices (OLEDs), which have received much attention in both academic and industrial fields. And in the past decade, some success has been achieved on the way this technology goes to highly profitable commercialization, for example, OLEDs have been applied in advanced displays for smart phones, televisions and digital cameras.

Iridium (iii) Complexes are a class of Phosphorescent materials that are widely used ("Synthesis and Characterization of Phosphorescent cyclic Iridium Complexes" target laser, peter djurvich, drew Murphy, feras Abdel-Razzaq, raymond Kwong, ira Tsyba, manfred Bortz, becky Mui, robert Bau, and Mark e.thompson organic Chemistry,2001vol.40, no.7, 1704-1711) although such organic luminescent materials have been commercialized in the manufacture of weather resistant OLED panels and lighting fixtures, these materials still have much room for improvement, such as reducing the cost of the material preparation process, improving the basic optoelectronic properties of the material, improving the quality of the final product application experience, reducing the cost of the materials kit in the device manufacturing process, and improving the overall resistance and the device integrity of the material after integration.

In the prior art, (WO 2015039723) discloses the synthesis of iridium complexes of polycyclic phenylpyridines and their use in organic opto-electronic devices; US20030072964, US20070087321 disclose organic phosphorescent materials with phenylisoquinoline as ligand; US20080261076 discloses heteroleptic complexes of Ir with 2-quinolinophenyl and 2-isoquinolinylphenyl as ligands for use as organic phosphorescent materials; US20120181511 discloses the use of iridium complexes of 5-substituted phenylquinolines in light emitting diodes, among others relating to diketone structures

An ancillary ligand phenylpyridine; CN107459535A discloses synthesis of iridium complexes of phenylpyridine mono-substituted at 3,4 or 5 positions and application of iridium complexes in organic photoelectric devices, the preparation method of the iridium complexes comprises 3,4 position substitution, 3,5 position substitution, 4,5 position substitution and 3,4,5 position substitution quinoline ligand coordination compounds, and an auxiliary ligand is a diketone structure. WO2013094620 discloses heteroleptic complexes of Ir coordinated with polysubstituted pyrazine ligands for use as organic phosphorescent red light materials; deep-red iridium complexes cyclometallated by phenyl anthridine derivatives for highlylefficient solution-processed organic light-emitting diode Bei Jiang, yu Gu, jing Qin, xiaoowen Ning, shaolong Gong, guohua Xie and Chuluo Yang Journal of Materials Chemistry C page 3492-3498 report Ir heteroleptic phosphorescent Materials for phenylphenanthridine ligands; the use of heteroleptic compounds of phenylquinoxaline-coordinated Ir in deep red to near infrared materials is reported by Highly efficient, deep-red organic light-emitting devices using energy transfer from exmaples Yuji Nagai, hisahiro Sasabe, jun Takahashi, a Natsuki Ouma, takasi Ito, a Satru Ohisaab and Junji Kido. US20080217606 discloses organic light emitting diode materials with phenylquinoline as ligand and pyridine imidazole and phenylpyridine imidazole as auxiliary ligands, the content of which is limited to simply substituted phenylquinoline ligands; US20080261076 discloses organic light emitting diode materials with phenylisoquinoline as a ligand and pyridine imidazole and phenylpyridine imidazole as ancillary ligands. Isotopic substitution can improve the performance of materials in applications, article SThe "deuterium effect" Ping Wang, fei-Fei Wang, yi Chen, qiang Niu, lei Lu, hong-Ming Wang, xi-Cun Gao, bin Wei, hong-Wei Wu, xin Caic and De-Chun ZouJ. Mater. Chem.C,2013,1,4821-4825 disclose that deuterated iridium complexes of triphenylpyridine have more stable electroluminescent effects. Patent CN107200755 discloses a scheme for improving performance of a phosphorescent material by a deuterated complex. Wherein the diketone structure->

The iridium complex coordinated by the auxiliary ligand has very good economic applicability and process operability when used as an organic luminescent material, and relatively more researches are carried out. Wherein for>

Study on deactivation mechanism of ligand-coordinated iridium complexes in OLED device application (Chemical Degradation in Organic Light-Emitting Devices: mechanisms and Implications for the Design of New Materials, susanna Schmidbauer, andrea Hohenleutner and Burkhard @>

Adv. Mater.2013,25, 2114-2129) reported->

The auxiliary ligand is easier to dissociate than other main ligands and leads to the inactivation of the iridium complex photoelectric functional material molecules. The patent CN108299510 discloses a->

Alternative ligand schemes for ancillary ligands.

The invention discloses a compound selectively containing deuterium substitution

Preparation method of iridium complex coordinated by auxiliary ligand and application of iridium complex coordinated by auxiliary ligand in electroluminescenceThe application of luminescent material and relevant photoelectric physical property. The preparative routes and methods involved therein are in the preparation of a class of polymers containing deuterium substitutions>

The iridium complex coordinated by the auxiliary ligand has the advantages of universality, high efficiency, proper mass production cost and the like. According to the invention, through ligand isotope modification of the organometallic complex of the cyclometalated iridium (III), the fluorescence quantum efficiency (PLQE) of luminescent material molecules can be improved, the stability of redox of the complex in the application process is improved, and the application stability of a material device can be definitely further improved. According to the spectral characteristics, electrochemical properties and compound modification functions of the molecules, the molecules can be used for preparing high-quality OLED related devices and application appliances.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: a deuterium-substituted organic metal complex, its preparing process and the relative application of said compound in electroluminescent material are disclosed.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

a deuterated iridium complex is provided, which has the following molecular structural formula:

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wherein

The moiety refers to the phenylisoquinoline ligand moiety that functions as the primary electron transition level,

refers to a single deuterated 1,3 dicarbonyl ancillary ligand moiety, ir ³⁺ The metal is a central coordination metal, ligands are all negative univalents, and Ir is positive trivalent;

wherein R is ^a 、R ^b Independently present hydrogen atoms, alkyl substituents which may be deuterated, partially deuterated, and aryl-substituted alkyl groups, and aryl substituents which may be deuterated, partially deuterated, and aryl groups containing alkyl or aryl substituents; r ^c A non-deuterated alkyl substituent.

Wherein the alkyl is a linear or branched alkyl having 2 to 6 carbon atoms and may include 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, 3,3-dimethyl-2-butyl.

When Rc is determined in the molecular structural formula,

can be the following six structures, respectively named as formula II, formula III, formula IV, formula V, formula VI and formula VII:

the deuterated iridium complex is an iridium complex Ir-2, ir-16, ir-23, ir-62 and Ir-71, and the specific structural formula is as follows:

the preparation method of the deuterated iridium complex at least comprises the following steps of: (1) Reacting a precursor substance with trivalent iridium to prepare a dimer; (2) The dimer is reacted with an ancillary ligand precursor compound and a deuterogen agent in one or two steps to obtain the compound of formula I; the chemical reaction equation is as follows:

the deuterated reagent comprises deuterated water, deuterated DMSO, deuterated methanol, deuterated ethanol, deuterated acetic acid, deuterated formic acid, deuterated sodium formate, deuterated benzene and deuterated DMF.

In addition, the invention also provides application of the deuterated iridium complex in electroluminescent materials, and particularly can be used for organic electronic components, such as organic electronic components which are organic light-emitting diodes, compact fluorescent lamps, incandescent lamps, organic photovoltaic cells, organic field effect transistors or light-emitting electrochemical cells. In particular organic optoelectronic light-emitting devices, can also be used as biomarkers or in imaging technology.

Compared with the prior art, the invention discloses a novel electroluminescent material, the stability of the compound is improved by introducing a specific site in a main ligand, the compound at least keeps the high-efficiency photoelectric conversion characteristic of the original complex (which is not deuterated), the light, electricity and heat stability of the compound are improved, and the compound can be used as a doped luminescent material applied to an appliance related to an electroluminescent device to prolong the service life of the appliance. The preparation route and the preparation method have the advantages of universality, high efficiency, proper mass production cost and the like in the aspect of preparing the iridium complex containing the deuterated diketone auxiliary ligand. According to the spectral characteristics and compound modification functions of the molecules, the molecules can be used for preparing high-quality organic electroluminescence related devices and application appliances.

Drawings

FIG. 1 is a structural diagram of an OLED using an iridium complex of a deuterated dione auxiliary ligand as an electroluminescent material;

FIG. 2 is a diagram of the deuterated complex Ir-62 and an iridium complex Ir (dmpiq) of a non-deuterated diketone ancillary ligand ₂ A divm photoluminescence spectrum contrast map;

FIG. 3 is a diagram of the deuterated complex Ir-62 and the iridium complex Ir (dmpiq) of a non-deuterated diketone ancillary ligand ₂ The divm is used as a red light doping material to prepare a luminescence spectrogram of a device;

FIG. 4 shows deuterated iridium complex Ir-62 and non-deuterated iridium complex at room temperatureIridium complex Ir (dmpiq) of deuterated diketone auxiliary ligand ₂ The luminous graph (4 a) and the voltage brightness change graph (4 b) of the OLED device prepared by using the divm as the red light doping material;

FIG. 5 shows deuterated iridium complex Ir-62 and iridium complex Ir (dmpiq) of non-deuterated diketone auxiliary ligand at room temperature ₂ The luminous current efficiency graph (5 a) and the power efficiency graph (5 b) of the OLED device prepared by using divm as the red light doping material;

FIG. 6 is a graph comparing the nuclear magnetic hydrogen spectrum of deuterated iridium complex Ir-23 with that of non-deuterated products;

FIG. 7 shows a nuclear magnetic hydrogen spectrum of a structural representation of a deuterated iridium complex Ir-62;

FIG. 8 shows a nuclear magnetic hydrogen spectrum of a structural representation of a deuterated iridium complex Ir-17;

FIG. 9 shows a nuclear magnetic hydrogen spectrum of a structural characterization of a deuterated iridium complex Ir-71;

FIG. 10 is an illustration of an ultra-high pressure high performance liquid chromatography purity and matching mass spectrometry detection of deuterated iridium complex Ir-62;

FIG. 11 is a mass spectrometric image of deuterated iridium complex Ir-17. Legend Ir-17 as a deuterated product;

FIG. 12 is a mass spectrometric image of deuterated iridium complex Ir-71. The legend illustrates Ir-71 as a deuterated product.

FIG. 13 is a plot of the decay of photoluminescence over time after deuterated complex Ir-62 and iridium complex Ir (dmpiq) 2divm with non-deuterated diketone ancillary ligands were used as red-light doped materials to fabricate OLED devices;

FIG. 14 is a drawing of deuterated iridium complex Ir-65 and an iridium complex Ir (dmpiq) of a non-deuterated diketone ancillary ligand ₂ The decay curve of the luminescence of the device prepared by divm with time;

fig. 15 is a graph showing lifetime tests of OLEDs prepared from deuterated iridium complex Ir-62 and iridium complex Ir (dmpiq) 2divm which is a non-deuterated diketone ancillary ligand.

Detailed Description

The technical scheme adopted by the invention is that a deuterated iridium complex with better stability, which is suitable for technical preparation, is provided, and has the following molecular structural formula:

wherein

Part refers to the 2-phenylisoquinoline ligand moiety (main ligand) acting as the predominant electron transition energy level>

Refers to a single deuterated 1,3 dicarbonyl ancillary ligand (ancillary ligand) moiety, ir ³⁺ Refers to a central coordination metal, the ligands are all negative univalents, and Ir is positive trivalent.

Wherein R is ^a 、R ^b The alkyl substituents can be deuterated, partially deuterated, and aryl-substituted alkyl groups, and the aryl substituents can be deuterated, partially deuterated, and aryl groups containing alkyl or aryl substituents, each independently present as hydrogen atoms. R ^c Is an alkyl substituent. The alkyl substituents can be deuterated, partially deuterated, and aryl-substituted alkyl.

Alkyl herein refers to straight or branched chain alkyl groups containing 2 to 6 carbon atoms and such alkyl groups may include 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, 3,3-dimethyl-2-butyl, and the like.

Molecular structural formula R of deuterated iridium complex ^c When the determination is made, the user can select the specific part,

the following six structures may be named as formula II, formula III, formula IV, formula V, formula VI and formula VII, respectively.

The formula I may be the following molecules Ir-1 toIr-90, but not limited to the molecules Ir-1 to Ir-90, the molecule Ir (pq) ₂ acac、Ir(dmpiq) ₂ divm is a conventional phosphorescent light-emitting molecule, and has a chemical structural formula shown in the following figure, wherein Ir (dmpiq) ₂ divm is a non-deuterated product of iridium complex Ir-62.

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Example 1 Synthesis and structural characterization of deuterated Iridium Complex Ir-62

And (3) synthesizing a dimer A. To a 75mL stopcock were added 1- (3,5-dimethylphenyl) isoquinoline (1.1g, 4.7 mmol), iridium trichloride trihydrate (332.6 mg, 0.9mmol), ethylene glycol ethyl ether (15 mL) and water (5 mL), and the atmosphere in the reaction flask was replaced with nitrogen. The reaction was heated to 100 ℃ and stirred for 12 hours. The reaction solution was cooled to room temperature, and a solid precipitated, washed with water, washed with ether, and dried to give dimer A (660mg, 45%).

Synthesis of Iridium Complex 62 (Ir-62) precursor. To a 15mL stopcock, dimer A (72.2mg, 0.05mmol), 2,8-dimethylnonane-4,6-dione (0.1 mL), sodium carbonate (26.5mg, 0.25mmol) and ethylene glycol ethyl ether (3 mL) were added, nitrogen bubbled for three minutes, and the reaction was heated at reflux for 12 hours. The reaction solution was cooled to room temperature, filtered, and the filtrate was spin-dried through a column (petroleum ether: ethyl acetate = 10). ¹ H NMR(300MHz,DMSO)δ8.92-8.89(m,2H),8.10(d,J＝6.3Hz,2H),8.02-7.99(m,2H),7.92(s,2H),7.81–7.78(m,4H),7.52(d,J＝6.3Hz,2H),6.45(s,2H),4.82(s,1H),2.29(s,6H),1.71–1.67(m,2H),1.56–1.49(m,2H),1.32(s,6H),1.25-1.13(m,2H),0.31(d,J＝6.6Hz,6H),-0.18(d,J＝6.6Hz,6H).MS(ESI):841.4[M+1] ⁺

And (3) synthesizing the deuterated iridium complex Ir-62. To a 15mL sealed tube were added the iridium complex 62 precursor (84.0 mg, 0.1mmol), sodium carbonate (26.5 mg, 0.25mmol), ethylene glycol ethyl ether (3 mL) and heavy water (0.1 mL), nitrogen was bubbled for three minutes, and the reaction was heated under reflux for 12 hours. The reaction solution was cooled to room temperature, filtered, and the filtrate was spin-dried over a column (petroleum ether: ethyl acetate = 10). FIG. 7 is a nuclear magnetic hydrogen spectrum of a structural characterization of the deuterated iridium complex Ir-62. ¹ H NMR(300MHz,CDCl ₃ )δ8.99-8.96(m,2H),8.24(d,J＝6.3Hz,2H),7.97(s,2H),7.83-7.79(m,2H),7.71-7.63(m,4H),7.23(d,J＝6.6Hz,2H),6.58(s,2H),4.80(s,0.06H),2.34(s,6H),1.82-1.76(m,2H),1.54-1.50(m,2H),1.45(s,6H),1.29(m,0H),0.33(d,J＝6.6Hz,6H),-0.13(d,J＝6.6Hz,6H).MS(ESI):842.4[M+1] ⁺ Emission peak in DCM at 625nm, FWHM =59nm, peak in PMMA at 629nm, FWHM =54nm. FIG. 10 is a chart of ultrahigh pressure high performance liquid chromatography purity and matching mass spectrometry detection of deuterated iridium complex Ir-62. Fig. 10 illustrates that the deuterium-substituted compound Ir-62 can be well purified, has good stability, and is suitable for controlling mass production processes, and finally, the high-purity organic photoelectric material chemical with electronic grade purity is obtained.

Example 2: synthesis and structural characterization of deuterated Ir-71

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And (4) synthesizing a dimer B. To a 75mL stopcock were added 1- (3,5-dimethylphenyl) -6-iso-tert-butylisoquinoline (1.16g, 4.0mmol), iridium trichloride trihydrate (282.6 mg, 0.8mmol), ethylene glycol ether (15 mL) and water (5 mL), and the atmosphere in the reaction flask was replaced with nitrogen. The reaction was heated to 100 ℃ and stirred for 12 hours. The reaction solution was cooled to room temperature, and a solid precipitated, washed with water, washed with ether, and dried to give dimer B (720mg, 45%).

Synthesis of iridium complex 71 precursor. To a 15mL stopcock, dimer B (160.7 mg, 0.1mmol), 2,8-dimethylnonane-4,6-dione (0.1 mL), sodium carbonate (53mg, 0.5mmol) and ethylene glycol ethyl ether (3 mL) were added, nitrogen bubbled for three minutes, and the reaction was heated at reflux for 12 hours. The reaction solution was cooled to room temperature, filtered, and the filtrate was spin-dried over a column (petroleum ether: ethyl acetate = 10). ¹ H NMR(500MHz,CDCl ₃ )δ8.88(d,J＝9.0Hz,2H),8.20(d,J＝6.5Hz,2H),7.97(s,2H),7.54(s,2H),7.49(d,J＝9.0Hz,2H),7.16(d,J＝6.5Hz,2H),6.57(s,2H),4.79(s,1H),2.70(d,J＝7.0Hz,4H),2.34(s,6H),2.07-2.04(m,2H),1.87-1.77(m,2H),1.54-1.52(m,2H),1.46(s,6H),1.33-1.30(m,2H),1.01-0.99(m,12H),0.33(d,J＝7.0Hz,6H),-0.11(d,J＝6.5Hz,6H).MS(ESI):953.6[M+1]

And (3) synthesizing a deuterated iridium complex 71. To a 15mL sealed tube were added the iridium complex 71 precursor (95.3mg, 0.1mmol), sodium carbonate (53mg, 0.5mmol), ethylene glycol ethyl ether (3 mL) and heavy water (0.2 mL), nitrogen was bubbled for three minutes, and the reaction was heated under reflux for 12 hours. The reaction solution was cooled to room temperature, filtered, and the filtrate was spin-dried over a column (petroleum ether: ethyl acetate = 10). FIG. 9 is a nuclear magnetic hydrogen spectrum of a structural characterization of the deuterated iridium complex Ir-71. ¹ H NMR(500MHz,CDCl ₃ )δ8.88(d,J＝8.5Hz,0H),8.20(d,J＝6.5Hz,2H),7.97(s,2H),7.54(s,2H),7.49(d,J＝8.5Hz,2H),7.16(d,J＝6.5Hz,2H),6.57(s,2H),2.71(d,J＝7.0Hz,4H),2.34(s,6H),2.08-2.03(m,2H),1.80-1.77(m,2H),1.53-1.51(m,2H),1.46(s,6H),1.34-1.30(m,2H),1.01-0.99(m,2H),0.33(d,J＝7.0Hz,6H),-0.11(d,J＝6.5Hz,6H).MS(ESI):954.4[M+1] ⁺ Emission peak in DCM at 619nm, FWHM =58nm, peak in PMMA at 622nm, FWHM =53nm. FIG. 12 is a mass spectrometric view of deuterated iridium complex Ir-71, illustrating Ir-71 as a deuterated product.

Example 3: synthesis and structural characterization of deuterated Ir-23

And (4) synthesizing the dimer C. To a 75mL sealed tube were added 1- (3,5-dimethylphenyl) -6-isopropylisoquinoline (1.10g, 4.0mmol), iridium trichloride trihydrate (282.6mg, 0.8mmol), ethylene glycol ether (15 mL) and water (5 mL), and the atmosphere in the reaction flask was replaced with nitrogen. The reaction was heated to 100 ℃ and stirred for 12 hours. The reaction solution was cooled to room temperature, and a solid precipitated, washed with water, ether and dried to give dimer C (700mg, 45%).

Synthesis of iridium complex Ir-23 precursor. To a 15mL sealed tube, dimer C (155.1mg, 0.1mmol), 3,7-diethyl-4,6-dione (0.1 mL), sodium carbonate (26.5mg, 0.25mmol) and ethylene glycol ethyl ether (3 mL) were added, nitrogen was bubbled for three minutes, and the reaction was heated under reflux for 12 hours. The reaction solution was cooled to room temperature, and spin-dried over a column (petroleum ether: ethyl acetate = 10) to obtain a red iridium complex Ir-23 precursor (110mg, 58%). ¹ H NMR(500MHz,CDCl ₃ )δ8.89(d,J＝8.5Hz,2H),8.16(d,J＝6.5Hz,2H),7.94(s,2H),7.58(s,2H),7.55(d,J＝9.0Hz,2H),7.11(d,J＝6.0Hz,2H),6.56(s,2H),4.80(s,1H),3.14-3.08(m,2H),2.33(s,6H),1.43(s,6H),1.38-1.36(m,12H),1.30-1.24(m,4H),1.11-1.05(m,2H),0.90-0.81(m,4H),0.42(t,J＝7.5Hz,6H),-0.16(t,J＝7.3Hz,6H).MS(ESI):953.4[M] ⁺

And (3) synthesizing the deuterated iridium complex Ir-23. To a 15mL sealed tube were added an iridium complex Ir-23 precursor (95.2mg, 0.1mmol), sodium carbonate (53mg, 0.5mmol), ethylene glycol ethyl ether (3 mL) and heavy water (0.2 mL), nitrogen was bubbled for three minutes, and the reaction system was heated under reflux for 12 hours. The reaction solution was cooled to room temperature, filtered, and the filtrate was spin-dried over a column (petroleum ether: ethyl acetate = 10)Iridium complex Ir-23 (80mg, 84%). ¹ H NMR(500MHz,CDCl ₃ )δ8.89(d,J＝9.0Hz,2H),8.16(d,J＝6.0Hz,2H),7.94(s,2H),7.58(s,2H),7.56(d,J＝9.0Hz,2H),7.11(d,J＝6.0Hz,2H),6.56(s,2H),4.80(s,1H),3.15-3.09(m,2H),2.35(s,6H),1.45(s,6H),1.40-1.38(m,12H),1.31-1.25(m,4H),1.12-1.07(m,2H),0.92-0.82(m,4H),0.42(t,J＝7.6Hz,6H),-0.16(t,J＝7.5Hz,6H).MS(ESI):954.4[M+1] ⁺ Emission peak in DCM at 620nm, FWHM =58nm, peak in PMMA at 621nm, FWHM =51nm. FIG. 6 is a graph comparing the nuclear magnetic hydrogen spectrum of deuterated iridium complex Ir-23 with that of non-deuterated products. The graph shows that the hydrogen (H) atoms at the designated positions can be converted into corresponding single isotope deuterium (D) atoms by adopting the method provided by the invention, and the deuteration rate of the final product is more than 99 percent.

Example 4: synthesis and structural characterization of deuterated Ir-17

Synthesis of iridium complex Ir-17 precursor. To a 15mL sealed tube, dimer A (134.4 mg, 0.1mmol), 3,7-diethyl-4,6-dione (0.1 mL), sodium carbonate (53mg, 0.5 mmol) and ethylene glycol ethyl ether (3 mL) were added, nitrogen was bubbled for three minutes, and the reaction was heated under reflux for 12 hours. The reaction solution was cooled to room temperature and spin-dried through a column (petroleum ether: ethyl acetate = 10) to obtain a red iridium complex Ir-17 precursor (140mg, 80%). ¹ H NMR(500MHz,CDCl ₃ )δ8.98(d,J＝8.0Hz,2H),8.22(d,J＝6.5Hz,2H),7.97(s,2H),7.80-7.79(m,2H),7.68-7.63(m,4H),7.17(d,J＝6.0Hz,2H),6.58(s,2H),4.82(s,1H),2.36(s,6H),1.60-1.53(m,2H),1.45(s,6H),1.32-1.26(m,2H),1.13-1.08(m,2H),0.91-0.84(m,4H),0.44(t,J＝7.5Hz,6H),-0.15(t,J＝7.5Hz,6H).MS(ESI):869.4[M+1] ⁺

And (3) synthesizing the deuterated iridium complex Ir-17. To a 15mL sealed tube were added iridium complex Ir-17 precursor iridium complex (86.9 mg, 0.1mmol), sodium carbonate (53mg, 0.5 mmol), ethylene glycol ethyl ether (3 mL) and heavy water (0.2 mL), nitrogen bubbling was carried out for three minutes, and the reaction was heated under reflux for 12 hours. The reaction solution was cooled to room temperature, filtered, and the filtrate was spin-dried over a column (petroleum ether: ethyl acetate = 10)Deuterated iridium complex Ir-17 (75mg, 86%). FIG. 8 is a nuclear magnetic hydrogen spectrum of a structural characterization of the deuterated iridium complex Ir-17. ¹ H NMR(500MHz,CDCl ₃ )δ8.98(d,J＝8.0Hz,2H),8.22(d,J＝6.0Hz,2H),7.97(s,2H),7.80-7.79(m,2H),7.68-7.63(m,4H),7.17(d,J＝6.0Hz,2H),6.58(s,2H),4.82(s,0.09H),2.36(s,6H),1.60-1.55(m,2H),1.45(s,6H),1.32-1.26(m,2H),1.13-1.08(m,2H),0.91-0.84(m,4H),0.44(t,J＝7.5Hz,6H),-0.14(t,J＝7.5Hz,6H).MS(ESI):870.4[M+1] ⁺ Emission peak in DCM at 626nm, FWHM =57nm, peak in PMMA at 626nm, FWHM =50nm. FIG. 11 is a mass spectrometric detection of deuterated iridium complex Ir-17, illustrating Ir-17 as a deuterated product.

Example 5: deuterated Ir-2 Synthesis and structural characterization

Synthesis of iridium complex Ir-2 precursor. To a 15mL sealed tube, dimer A (134.4 mg, 0.1mmol), 3,7-dimethyl-4,6-dione (0.1 mL), sodium carbonate (53mg, 0.5 mmol), ethylene glycol ethyl ether (3 mL), nitrogen bubbling was carried out for three minutes, and the reaction was heated under reflux for 12 hours. The reaction solution was cooled to room temperature, and spin-dried over a column (petroleum ether: ethyl acetate = 10) to obtain a red iridium complex Ir-2 precursor (130mg, 77%). ¹ H NMR(500MHz,CDCl ₃ )δ8.99(d,J＝7.0Hz,2H),8.20-8.16(m,2H),7.96(s,2H),7.80(d,J＝8.0Hz,2H),7.67-7.63(m,4H),7.18(d,J＝6.0Hz,2H),6.59(s,2H),4.79(t,J＝6.0Hz,1H),2.36(s,6H),1.81-1.74(m,2H),1.47(s,6H),1.23-1.19(m,1H),1.02-0.97(m,1H),0.88-0.84(m,1H),0.78-0.77(m,3H),0.75-0.70(m,1H),0.37-0.32(m,6H),-0.17--0.21(m,3H).MS(ESI):841.4[M+1]

And (3) synthesizing the deuterated iridium complex Ir-2. To a 15mL sealed tube were added iridium complex Ir-2 precursor (84.4 mg, 0.1mmol), sodium carbonate (53mg, 0.5 mmol), ethylene glycol ethyl ether (3 mL) and heavy water (0.2 mL), nitrogen was bubbled for three minutes, and the reaction was heated under reflux for 12 hours. The reaction solution was cooled to room temperature, filtered, and the filtrate was spin-dried through a column (petroleum ether: ethyl acetate = 10). ¹ H NMR(500MHz,CDCl ₃ )δ8.99(d,J＝7.0Hz,2H),8.20-8.17(m,2H),7.96(s,2H),7.80(d,J＝7.5Hz,2H),7.69-7.63(m,4H),7.18(d,J＝6.5Hz,2H),6.58(s,2H),2.36(s,6H),1.81-1.74(m,2H),1.47(s,6H),1.23-1.19(m,1H),1.03-0.97(m,1H),0.90-0.82(m,1H),0.77(d,J＝7.0Hz,3H),0.74-0.70(m,1H),0.37-0.32(m,6H),-0.17--0.21(m,3H).MS(ESI):842.4[M+1] ⁺ Emission peak in DCM at 627nm,FWHM＝60nm,peak in PMMA at 627nm,FWHM＝52nm。

Example 6 deuterated iridium complex material characterization test

Comparing the optical properties of the deuterated iridium complex, the test method comprises the following steps: the band gap (Eg) and LUMO values of the materials were measured using Cyclic Voltammetry (CV). The whole test process is carried out on CHI600D electrochemical workstation (Shanghai Chenghua apparatus Co.) in glove box (Lab 2000, etelux), pt column is used as working electrode, ag/AgCl is used as reference electrode, pt wire is used as auxiliary electrode to form three-electrode system, and the medium adopted in the test process is 0.1M tetrabutylammonium hexafluorophosphate (Bu) ₄ NPF ₆ ) The measured potentials were measured with ferrocene (Fc) added as an internal standard. The HOMO value of the material was directly measured by a Model IPS-4Ionization Energy Measurement System. The fluorescence quantum efficiency (PLQE) of the material is based on the formula

(wherein:. Phi.) _s Is the fluorescence quantum yield, Φ, of the sample _r Is the fluorescence quantum yield of the standard, eta is the refractive index of the solution, A _s And A _r Is the absorption value at the fluorescence excitation wavelength of the sample and the standard sample I _s And I _r Is the integrated area of the fluorescence of the sample and the standard sample) is calculated by a relative method. The materials and a standard with a known quantum yield were prepared as a chloroform solution of polymethyl methacrylate (PMMA) at the same concentration, spin-coated to form a film, and under the same measurement conditions, an ultraviolet absorption spectrum (GENESYS 10s, thermo) and a fluorescence spectrum (F97 pro fluorescence spectrophotometer, prism technique) were measured. The photon energy (ET 1) of the material is calculated from the formula E = h ν =1240/λ (where λ is the tangential wavelength of the starting position of the fluorescence spectrum of the PMMA film of the material). As can be seen from Table 1 below, deuteriumCompared with non-deuterated iridium complexes, the fluorescent quantum efficiency of the substituted iridium complex material is improved.

TABLE 1

^a Measured by cyclic voltammetry ^b Energy of triplet state ^c PLQE efficiency in Ir (PQ) ₂ (acac) luminous efficiency at 298K was one unit of a reference value.

Example 7

The deuterated iridium complex is doped into a host material as a luminescent material to prepare the device OLED, and the structure of the OLED device is shown in figure 1. Wherein the Cathode is 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 deuterated diketone auxiliary ligand coordinated iridium complex Ir-62 is used as an electroluminescent material and contained in an EML (light-emitting layer), and the light-emitting layer comprises a host material and a light-emitting material. Deuterated iridium complex Ir-62 and an iridium complex Ir (dmpiq) of a non-deuterated diketone auxiliary ligand ₂ And comparing the parameters of the light-emitting performance and the like after the divm is applied to the device.

Wherein, FIG. 2 shows deuterated complex Ir-62 and iridium complex Ir (dmpiq) of non-deuterated diketone auxiliary ligand ₂ divm photoluminescence spectra contrast. As can be seen from FIG. 2, the two materials have completely consistent emission spectra, and the saturated red light device can be prepared in the red region of the fluorescence spectrum.

FIG. 3 is an illustration of an iridium complex Ir (dmpiq) with deuterated complex Ir-62 and non-deuterated diketone ancillary ligands ₂ And the divm is used as a luminescence spectrum of the red light doping material prepared into the OLED device. The emission spectrum of the OLED with the same structure as shown in fig. 3 is substantially identical in appearance under the same test conditions, but the emission intensity is different, wherein the OLED containing the deuterated product Ir-62 has higher electroluminescence intensity under the same conditions, and the spectrum wavelength is 625nm and is red-shifted from its peak in PMMA.

FIG. 4 shows deuterated iridium complex Ir-62 and non-deuterated diketone co-catalyst at room temperatureIridium complex Ir (dmpiq) of co-ligand ₂ The divm is used as a light-emitting graph (J-V) and a voltage brightness change graph (V-L) of an OLED device prepared by the red light doping material, current and voltage curves of the device under the same structure are basically consistent under the same test condition, and the voltage brightness curve shows that the device corresponding to Ir-62 has higher brightness under the same voltage. The starting voltage is below 3V, which shows that the core luminescent material has very good luminescent property and stability in the luminescent process.

FIG. 5 shows deuterated iridium complex Ir-62 and iridium complex Ir (dmpiq) of non-deuterated diketone auxiliary ligand at room temperature ₂ The luminous current efficiency graph (5 a) and the power efficiency graph (5 b) of the OLED device prepared by using divm as the red light doping material. As can be seen from the figure, the OLED device prepared by the deuterated iridium complex Ir-62 has higher current efficiency>24cd/A, higher luminous efficiency>25cd/W。

FIG. 13 is an illustration of an iridium complex Ir (dmpiq) of deuterated complex Ir-62 and a non-deuterated diketone ancillary ligand ₂ The decay curve of photoluminescence with time after the divm is used as a red light doping material to prepare an OLED device. The attenuation test is to pass 0.3mW/m ² The ultraviolet light irradiates a stable polystyrene high molecular film doped with 5% of iridium complex, the photoluminescence intensity is recorded, and the function relation between the luminous decay and the time of the compound is finally obtained. FIG. 13 shows that the luminescence intensity of the deuterated complex Ir-62 is maintained significantly higher than that of the non-deuterated material Ir (dmpiq) ₂ divm, which decays more slowly in photoluminescence, has better optical stability. After illumination for 400 minutes, the retention degree of the luminous intensity is 7-8% higher than that of the non-deuterated material.

FIG. 14 deuterated Iridium complex Ir-62 and Iridium complex Ir (dmpiq) of a non-deuterated Dione ancillary ligand ₂ Photoluminescence decay curves over time for devices prepared from divm. The device structure was ITO/HT 17H 09 (5%, 10 nm)/HT 17 (150 nm)/PH 315 RD (2%, 20 nm)/ET 15 (60 nm)/E02 (2 nm)/Al (120 nm), where RD represents Ir-62 and a comparative non-deuterated iridium complex Ir (dmpiq) 2divm of the same structure. The initial current density of the electroluminescence decay test was 50mA/cm2. The graph shows that the decay rate of the deuterated Ir-62 device is significantly lower than that of the non-deuterated Ir (dmpiq) ₂ divm, which decays more slowly in electroluminescence, has better device stability. LT97@50mA/cm ² The service lives of the two materials are respectively 78.6 hours and 30.9 hours, and the device made of the material Ir-62 with the coordination of the deuterated diketone auxiliary ligand is obviously superior to a non-deuterated conventional material.

FIG. 15 is a schematic representation of the deuterated iridium complex Ir-62 and an iridium complex Ir (dmpiq) of a non-deuterated diketone ancillary ligand ₂ The service life test of the OLED service life test chart prepared by divm uses a ZJLS-4 type service life tester of the luminous and photoelectric research room of Shanghai university, and the service life of an OLED device is tested in real time by driving in a constant current mode. In this experiment, the current density was constant (50 mA cm) ^-2 ) The luminance and voltage of the device are measured as a function of time. As can be seen from the test results shown in fig. 15A, the stability of the OLED device prepared by the deuterated iridium complex compound is better, and the luminance decay is slower than that of the non-deuterated iridium complex compound along with the change of time; as can be seen from fig. 15B, the voltage of the OLED device prepared from the deuterated iridium complex compound increases more slowly than that of the non-deuterated iridium complex compound with time, and no increase indicates that the device does not attenuate, and an increase in the voltage indicates that the device has a poorer effect. Therefore, the device made of the deuterated material has lower voltage change and better use effect.

Example 8

Preparing a device from the deuterated iridium complex and the iridium complex of the non-deuterated diketone auxiliary ligand, and testing relevant data of the device, wherein the data comparison test results are shown in the following table 2:

TABLE 2

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As shown in Table 2, the electroluminescent wavelength of the device is mainly determined by photoluminescence of the Ir complex per se through comparison of device data, and the efficiency of the device is consistent with the PLQE trend of the Ir complex per se under the same condition. Therefore, the disclosed deuterated iridium complex compound with high PLQE can obtain high device efficiency in other devices. Compared with non-deuterated compounds, the deuterated iridium complex compounds have obviously improved partial product Current Efficiency (CE) and External Quantum Efficiency (EQE), such as Ir-2 and Ir-62; the partial product efficiency is not obviously changed before and after deuteration, such as Ir-23; compared with a non-deuterated compound, the deuterated iridium compound has the advantages that the service life of all devices is obviously prolonged, the improvement range is 15-30%, and the deuterated iridium compound is used as a luminescent material for manufacturing OLED devices and related equipment, and has the advantage of obviously prolonging the service life compared with the conventional non-deuterated iridium compound;

the foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims

1. The deuterated iridium complex is characterized by being iridium complexes Ir-2, ir-16, ir-23, ir-62 and Ir-71, and having a specific structural formula as follows:

2. a method for synthesizing the deuterated iridium complexes Ir-2, ir-16, ir-23, ir-62 and Ir-71 as described in claim 1, wherein the synthetic routes are respectively as follows:

the synthesis method of the deuterated iridium complex 62 comprises the following steps:

(1) Synthesizing a dimer A, namely adding 1- (3,5-dimethylphenyl) isoquinoline, iridium trichloride trihydrate, ethylene glycol ethyl ether and water into a 75ml sealed tube, replacing the atmosphere of a reaction bottle with nitrogen, heating and stirring a reaction system, cooling the reaction system to room temperature, separating out a solid, washing with water, washing with ethyl ether, and drying to obtain the dimer A;

(2) Synthesizing an iridium complex 62 precursor, namely adding dimer A,2,8-dimethyl nonane-4,6-diketone, sodium carbonate and ethylene glycol ethyl ether into a sealed tube, bubbling nitrogen, heating and refluxing a reaction system, cooling the reaction system to room temperature, filtering, and spin-drying filtrate to pass through a column to obtain an iridium complex 62;

(3) Synthesizing a deuterated iridium complex Ir-62, namely adding the iridium complex 62, sodium carbonate, ethylene glycol ethyl ether and heavy water into a sealed tube, bubbling nitrogen, heating and refluxing a reaction system, cooling the reaction system to room temperature, filtering, and spin-drying filtrate and passing the filtrate through a column to obtain the deuterated iridium complex Ir-62;

the synthesis method of the deuterated Ir-71 comprises the following steps:

(1) Synthesizing a dimer B, namely adding 1- (3,5-dimethylphenyl) -6-iso-tert-butyl isoquinoline, iridium trichloride trihydrate, ethylene glycol ethyl ether and water into a sealed tube, replacing the atmosphere of a reaction bottle with nitrogen, heating and stirring a reaction system, cooling the reaction system to room temperature, separating out a solid, washing with water, washing with diethyl ether, and drying to obtain the dimer B;

(2) Synthesizing an iridium complex 71 precursor, namely adding dimer B,2,8-dimethyl nonane-4,6-diketone, sodium carbonate and ethylene glycol ethyl ether into a sealed tube, bubbling nitrogen, heating and refluxing a reaction system, cooling the reaction system to room temperature, filtering, and spin-drying filtrate and passing the filtrate through a column to obtain the iridium complex 71 precursor;

(3) Synthesizing a deuterated iridium complex 71, namely adding an iridium complex 71 precursor, sodium carbonate, ethylene glycol ethyl ether and heavy water into a sealed tube, bubbling nitrogen, heating and refluxing a reaction system, cooling the reaction system to room temperature, filtering, and spin-drying filtrate and passing the filtrate through a column to obtain the deuterated iridium complex 71;

synthesis method of deuterated Ir-23

(1) Synthesizing a dimer C, namely adding 1- (3,5-dimethylphenyl) -6-isopropylisoquinoline, iridium trichloride trihydrate, ethylene glycol ethyl ether and water into a sealed tube, replacing the atmosphere of a reaction bottle with nitrogen, heating and stirring a reaction system, cooling the reaction system to room temperature, separating out solids, washing with water, washing with ether, and drying to obtain the dimer C;

(2) Synthesizing an iridium complex Ir-23 precursor, namely adding dimer C,3,7-diethyl-4,6-diketone, sodium carbonate and ethylene glycol ethyl ether into a sealed tube, bubbling nitrogen, heating and refluxing a reaction system, cooling the reaction system to room temperature, and spin-drying and passing through a column to obtain the iridium complex Ir-23 precursor;

(3) Synthesizing a deuterated iridium complex Ir-23, namely adding an iridium complex Ir-23 precursor, sodium carbonate, ethylene glycol ethyl ether and heavy water into a sealed tube, bubbling nitrogen, heating and refluxing a reaction system, cooling the reaction liquid to room temperature, filtering, and spin-drying filtrate to pass through a column to obtain the deuterated iridium complex Ir-23;

the synthesis method of the deuterated Ir-17 comprises the following steps:

(1) Synthesizing a dimer A, namely adding 1- (3,5-dimethylphenyl) isoquinoline, iridium trichloride trihydrate, ethylene glycol ethyl ether and water into a 75ml sealed tube, replacing the atmosphere of a reaction bottle with nitrogen, heating and stirring a reaction system, cooling the reaction system to room temperature, separating out a solid, washing with water, washing with diethyl ether, drying to obtain a dimer A (2) iridium complex Ir-17 precursor, adding dimer A,3,7-diethyl-4,6-diketone, sodium carbonate, ethylene glycol ethyl ether and nitrogen bubbling, heating and refluxing the reaction system, cooling the reaction system to room temperature, and spin-drying to pass through a column to obtain an iridium complex Ir-17 precursor;

(3) Synthesizing a deuterated iridium complex Ir-17, namely adding an iridium complex Ir-17 precursor, sodium carbonate, ethylene glycol ethyl ether and heavy water into a sealed tube, bubbling nitrogen, heating and refluxing a reaction system, cooling the reaction system to room temperature, filtering, and spin-drying filtrate and passing the filtrate through a column to obtain the deuterated iridium complex Ir-17;

the synthesis method of deuterated Ir-2 comprises the following steps:

(1) Synthesizing a dimer A, namely adding 1- (3,5-dimethylphenyl) isoquinoline, iridium trichloride trihydrate, ethylene glycol ethyl ether and water into a 75ml sealed tube, replacing the atmosphere of a reaction bottle with nitrogen, heating and stirring a reaction system, cooling the reaction system to room temperature, separating out a solid, washing with water, washing with diethyl ether, drying to obtain a dimer A (2) iridium complex Ir-2 precursor, adding the dimer A,3,7-dimethyl-4,6-diketone, sodium carbonate, ethylene glycol ethyl ether and nitrogen bubbling, heating and refluxing the reaction system, cooling the reaction system to room temperature, and spin-drying the iridium complex Ir-2 precursor passing through a column;

(3) And (3) synthesizing the deuterated iridium complex Ir-2, namely adding an iridium complex Ir-2 precursor, sodium carbonate, ethylene glycol ethyl ether and heavy water into a sealed tube, bubbling nitrogen, heating and refluxing a reaction system, cooling the reaction solution to room temperature, filtering, and spin-drying filtrate to pass through a column to obtain the deuterated iridium complex Ir-2.

3. Use of the deuterated iridium complex as defined in claim 1 in electroluminescent materials.

4. The deuterated iridium complex as recited in claim 1 is used as an electroluminescent material in photoelectric appliances.