Iridium complex containing rosin-based ligand, preparation method and application thereof

Abstract

The present invention discloses an iridium complex containing a rosin-based ligand, its preparation method, and application, belonging to the field of organic optoelectronic materials. The iridium complex containing a rosin-based ligand solves the problems of existing chiral iridium complexes, such as the high cost of stable chirally pure raw materials, the easy racemization of chiral molecules, and the high cost of chiral resolution. It offers the advantages of environmental sustainability, ease of preparation, and low cost. The preparation steps include reacting a rosin-based ligand with an iridium intermediate under alkaline conditions to obtain the target product.

Description

Technical Field

[0001] The present invention relates to a circularly polarized electroluminescent material, in particular to an iridium complex phosphorescent material containing a rosin-based ligand and a preparation method and application thereof. Background Art

[0002] Circularly polarized electroluminescence has great application potential in future 3D displays and photonic technologies. The most direct way to achieve circularly polarized electroluminescence is to use chiral electroluminescent materials. Cyclometallic iridium complexes are spherical and not easily quenched by concentration. They have the advantages of high efficiency (theoretical electroluminescence internal quantum efficiency is 100%), short excited state lifetime, and strong color tunability. A large number of studies have shown that among many heavy metal complexes, iridium complexes are considered to be the most ideal choice for phosphorescent materials of organic electroluminescent devices (OLEDs), and research has also been done on circularly polarized electroluminescence. The asymmetry factor ( g em =2( I L - I R ) / ( I L + I R ), I L and I R The circularly polarized luminescence performance is evaluated by the absolute value of left-handed and right-handed light intensities, respectively. The maximum absolute value is 2. The typical asymmetry factor of iridium complexes is 10 -3 However, the stable chiral raw materials currently used are generally expensive, and readily available chiral raw materials are prone to racemization during reactions and device preparation, losing their circularly polarized luminescence activity. Racemic compounds with newly constructed chiral centers often lack active sites for chemical resolution and can only be resolved using chiral columns. Furthermore, chiral columns are extremely expensive. Currently, a chiral column with a single separation capacity of around 100 mg costs around 100,000 yuan, making it unaffordable for ordinary laboratories and making their commercialization prospects even slimmer.

[0003] After searching, the Chinese patent application number is 202310090362.3, and the application publication date is June 2, 2023. The application discloses an ionic metal iridium complex and its preparation method and application. Chiral camphorsulfonate anions are introduced into the ionic metal iridium complex of this material. Under the drive of the electric field, the migration and accumulation of chiral anions lead to an increase in the chirality of the film, and further transfer to cationic excitons to emit circularly polarized light, so that the material shows electrically amplified circularly polarized luminescence. However, the maximum external quantum efficiency of the electrochemical cell made of this ionic metal iridium complex is low, and the luminescence asymmetry factor needs to be improved.

[0004] Therefore, how to design a chiral iridium complex with easy-to-obtain raw materials, low cost and good circularly polarized luminescence performance for producing OLEDs is a difficulty that needs to be solved urgently. Summary of the Invention

[0005] 1. Problem to be solved

[0006] The present application provides an iridium complex containing a rosin-based ligand, the purpose of which is to obtain an iridium complex with readily available raw materials and low preparation cost, while also having good circularly polarized electroluminescent performance when used to prepare OLEDs.

[0007] 2. Technical Solution

[0008] In order to solve the above problems, the technical solutions adopted by the present invention are as follows:

[0009] To address the problems of expensive chiral raw materials and difficult chiral separation of existing chiral iridium complexes, the present invention provides a cyclometallated iridium complex containing a rosin-based ligand. The chirality of the rosin-based ligand is utilized to induce the complex to produce circularly polarized electroluminescence. At the same time, the steric hindrance of the rosin group is utilized to reduce the interaction between the complex molecules and reduce the concentration quenching effect of the complex.

[0010] An iridium complex containing a rosin-based ligand, the general structural formula of this type of complex is as follows:

[0011] ;

[0012] In the formula, R1 is an alkyl group or a fluoroalkyl group containing 1 to 8 carbon atoms; the structural formula of R2 is or ; When R2 is R2H, its structural formula is or .

[0013] Dehydroabietic acid (DHAA) is a natural chiral tricyclic diterpenoid compound containing three chiral carbon atoms. It is a key product of the rosin chemical industry and is inexpensive. It possesses unique physicochemical properties not found in other rosin derivatives, such as stable properties, strong antioxidant capacity, and a large specific rotation. However, due to steric hindrance, the carboxyl groups in rosin have a weak coordination ability, making direct coordination difficult. Even if coordination is achieved, the product is unstable and has poor performance. Similarly, due to steric hindrance, the carboxyl groups in rosin have very poor reactivity and are not easily converted into other groups. Consequently, rosin is difficult to modify into ligands with strong coordination ability, and there are currently no reports of rosin groups being used as chiral ligands. Therefore, how to introduce rosin-based ligands into iridium complexes is a major challenge.

[0014] A method for preparing an iridium complex containing a rosin-based ligand, comprising the following steps:

[0015] The iridium complex chlorine bridge intermediate and the rosin-based diketone ligand are dissolved in an organic solvent, and a dissociation reaction is carried out at 0-200° C. in the presence of a base for 1-24 hours to obtain the target product.

[0016] Furthermore, the iridium complex chlorine bridge intermediate is Ir1 or Ir2, and its structural formula is as follows:

[0017] .

[0018] Furthermore, the structural formula of the rosin-based diketone ligand is:

[0019] .

[0020] Furthermore, the preparation method of the rosin-based ligand is as follows: NaH and a rosin-based derivative are mixed in an organic solvent, ice-bathed in a nitrogen environment for a period of time, and then a fluoroalkyl ester compound is added, and the temperature is raised to 20-150° C. to obtain the rosin-based ligand.

[0021] Furthermore, the base includes one or a mixture of two or more of sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, sodium hydride, sodium ethoxide, triethylamine, pyridine, dibutylamine, piperidine, and piperazine; and the organic solvent includes one or a mixture of two or more of dichloromethane, chloroform, 1,2-dichloroethane, carbon tetrachloride, o-dichlorobenzene, and toluene.

[0022] Furthermore, the molar fractions of each reactant in the reaction system are:

[0023] 1 part of iridium complex chlorine bridge intermediate;

[0024] 2-4 parts of rosin-based diketone ligand;

[0025] 1-6 parts of alkali;

[0026] 50-500 parts of organic solvent.

[0027] Application of the above-mentioned iridium complex containing rosin-based ligand as or in the preparation of circularly polarized electroluminescent materials.

[0028] Application of the above-mentioned iridium complex containing rosin-based ligands in the preparation of organic circularly polarized light-emitting diode devices.

[0029] The above-mentioned organic circularly polarized light-emitting diode device structure comprises a cathode, an anode and an organic thin film layer;

[0030] The organic thin film layer is a light-emitting layer containing a light-emitting material and located between the cathode and the anode;

[0031] The luminescent material used in the luminescent layer includes the iridium complex containing the rosin-based ligand.

[0032] 3. Beneficial effects

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] (1) The present invention uses biomass rosin as raw material and utilizes the characteristics of dehydroabietic acid containing three stable chiral carbon atoms to solve the problems of high cost of stable chiral pure raw materials, easy racemization of chiral molecules, and high cost of chiral separation. Dehydroabietic acid also uses the relatively rigid alicyclic steric structure to reduce intermolecular interactions without significantly reducing the luminous efficiency of the molecules. This type of complex promotes the low-cost and green sustainable development of circularly polarized electroluminescent materials, which is conducive to its practical promotion and the high-value utilization of rosin.

[0035] The present invention forms a carbon-iridium bond with the iridium atom through the R2 group to generate a metal organic complex, which improves the electroluminescent efficiency of the complex and plays a major role in the light color. The rosin-based ligand mainly transfers chirality to give the complex circularly polarized luminescence properties, plays a role in fine-tuning the light color, and reduces the concentration quenching of the complex molecules.

[0036] (2) The photoelectric properties of the iridium complex containing rosin-based ligands of the present invention are excellent, taking into account both the luminescence quantum efficiency and the asymmetry factor, with a medium to high luminescence quantum efficiency and a 10 -3 The typical asymmetry factor is of the order of magnitude, which has the potential to be applied in circularly polarized electroluminescence. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 1 is a single crystal structure diagram of the iridium complex IrS2 in the present invention;

[0038] Figure 2 is the UV-visible absorption spectrum of the iridium complex IrS1-IrS3 in dichloromethane solution;

[0039] Figure 3 is the photoluminescence spectrum of the iridium complex IrS1-IrS3 in dichloromethane solution in the present invention;

[0040] Figure 4 is the UV-visible absorption spectrum of the iridium complexes IrBS1-IrBS3 in dichloromethane solution;

[0041] Figure 5 1 is the photoluminescence spectrum of the iridium complexes IrBS1-IrBS3 in the present invention in dichloromethane solution. DETAILED DESCRIPTION

[0042] The present invention will be further described below with reference to specific embodiments.

[0043] The raw materials S0, iridium intermediates Ir1 and Ir2 used in the specific embodiment are as described in the literature ( Monatsh. Chem. ,2008, 139, 697; J. Mater. Chem. C , 2020, 8, 6168; J. Mater. Chem. C , 2024, 12,3997) method synthesis.

[0044] Example 1

[0045] NaH (1.2 g, 50 mmol) was weighed and added to a 250 ml round-bottom flask. The flask was evacuated and filled with N2 gas. After an ice bath for 5 minutes, THF (50 mL) and raw material S0 (3 g, 10 mmol) were injected. After continuing the ice bath for 30 minutes, ethyl trifluoroacetate (18 mL, 150 mmol) was injected. After stabilization, the temperature was raised to 80 °C and the reaction was allowed to proceed overnight. After the reaction was completed, the flask was quenched with ethanol in an ice bath. The pH was adjusted to neutral with dilute hydrochloric acid, and the organic phase was extracted with dichloromethane. The solvent was evaporated under reduced pressure and purified on a silica gel column with dichloromethane and petroleum ether (1:1) to obtain 2.74 g of yellow oily product S1 with a yield of 69.1%.

[0046]

[0047] 1 H NMR (400 MHz, CDCl3) δ 15.15 (br, 1H), 7.19 (d, J = 8.2 Hz, 1H), 7.03(dd, J = 8.2, 1.5 Hz, 1H), 6.90 (s, 1H), 6.17 (s, 1H), 2.89-2.80 (m, 3H), 2.37(d, J = 12.8 Hz, 1H), 2.15 (dd, J = 12.6, 2.1 Hz, 1H), 1.89-1.76 (m, 3H), 1.72(dd, J = 12.9, 4.2 Hz, 1H), 1.59-1.51 (m, 2H), 1.42-1.36 (m, 1H), 1.28 (s, 3H),1.26 (s, 3H), 1.23 (d, J = 6.9 Hz, 6H). 19F NMR (377 MHz, CDCl3) δ -75.95 (s,3F). HRMS ((+)-ESI): m / z = 416.1890 (calcd. 416.1939for [C 23 H 29 F3NaO2] [M+Na + ]).

[0048] Under the same conditions, ethyl trifluoroacetate was replaced with ethyl pentafluoropropionate to obtain yellow oily product S2 with a yield of 66.7%.

[0049]

[0050] 1 H NMR (400 MHz, CDCl3) δ 15.33 (br, 1H), 7.19 (d, J = 8.2 Hz, 1H), 7.03(d, J = 7.9 Hz, 1H), 6.91 (s, 1H), 6.23 (s, 1H), 2.88-2.82 (m, 3H), 2.37 (d, J =12.9 Hz, 1H), 2.15 (dd, J = 12.6, 1.9 Hz, 1H), 1.89-1.77 (m, 3H), 1.71 (dd, J =4.8, 4.2 Hz, 1H), 1.61 -1.51 (m, 2H), 1.44-1.38 (m,1H), 1.29 (s, 3H), 1.26(s, 3H), 1.24 (d, J = 6.9 Hz, 6H). 19 F NMR (377 MHz, CDCl3) δ -82.80 (s, 3F), -123.76 (s, 2F). HRMS ((+)-ESI): m / z = 445.2168 (calcd. 445.2166 for [C 24 H 30 F5O2][M+H + ]).

[0051] Under the same conditions, ethyl trifluoroacetate was replaced with ethyl heptafluorobutyrate to obtain yellow oily product S3 with a yield of 67.3%.

[0052]

[0053] 1 H NMR (400 MHz, CDCl3) δ 15.34 (br, 1H), 7.21 (d, J = 8.3 Hz, 1H), 7.05(dd, J = 8.2, 2.1 Hz, 1H), 6.92 (s, 1H), 6.23 (s, 1H), 2.89-2.84 (m, 3H), 2.39(d, J = 12.8 Hz, 1H), 2.17 (dd, J = 12.5, 2.1 Hz, 1H), 1.88-1.78 (m, 3H),1.73(dd, J = 13.0, 4.5 Hz, 1H), 1.62-1.56 (m, 2H), 1.35-1.39(m, J = 13.6 Hz, 1H), 1.31 (s,3H), 1.28 (s, 3H), 1.26 (d, J = 7.04 Hz, 6H). 19 F NMR (376 MHz, CDCl3) δ -80.57(d, J = 17.7 Hz, 3F), -121.39 – -121.71 (m, 2F), -126.94 (s, 2F). HRMS ((+)-ESI): m / z = 495.2180 (calcd. 495.2134 for [C 25 H 30 F7O2] [M+H + ]).

[0054] Example 2

[0055] Ir1 (40 mg, 0.02 mmol), S1 (16 mg, 0.04 mmol), and anhydrous sodium carbonate (7 mg, 66.04 mmol) were placed in a 100 mL round-bottom flask and dissolved in 30 mL of dichloromethane. The reaction apparatus was sealed, evacuated, and filled with nitrogen. The temperature was raised to 50 °C and the reaction was allowed to proceed for 12 h. After the reaction was completed, the organic phase was extracted with dichloromethane and water, and then purified by column chromatography with dichloromethane and petroleum ether (1:1) to obtain an orange-red solid of IrS1 with a yield of 22.6%.

[0056] NMR of the product: 1 H NMR (400 MHz, CDCl3) δ 8.37 (d, J= 8.5 Hz, 2H), 8.10 (d, J = 8.9 Hz, 2H), 7.89 (s, 1H), 7.75 (s, 2H), 7.65 (s, 2H), 7.45 (d, J = 1.8 Hz,2H), 7.33 (s, 2H), 7.09 (s, 1H), 7.03 (s, 1H), 6.87 (s, 1H), 6.69 (d, J = 7.9Hz, 2H), 6.58 (d, J = 2.9 Hz, 2H), 6.40 (s, 1H), 3.36 (d, J = 23.6 Hz, 2H), 3.22(d, J = 10.8 Hz, 2H), 3.12 (s, 3H), 2.97 (d, J = 13.3 Hz, 3H), 2.93 (d, J = 6.0 Hz,2H), 2.42 (d, J = 8.0 Hz, 1H), 2.17 (d, J = 13.3 Hz, 2H), 1.92 (s, 1H), 1.57 (s,3H), 1.38 (s, 3H), 1.37 (s, 3H), 1.35 (d, J = 3.8 Hz, 6H). 19 F NMR (376 MHz, CDCl3) δ -75.29 (s, 3F).

[0057] Product mass spectrum: HRMS ((+)-ESI): m / z = 1047.3602 (calcd. 1047.3688 for [C 57 H 54 F3IrN2O2] [M+H + ]). The reaction formula is as follows:

[0058]

[0059] The luminescence quantum efficiency of IrS1 in PMMA film is 43% when the mass percentage concentration is 1%. The UV-visible absorption spectrum and photoluminescence spectrum in dichloromethane solution are as follows: Figure 2 and Figure 3 shown.

[0060] Example 3

[0061] Ir1 (40 mg, 0.02 mmol), S2 (22 mg, 0.05 mmol), and anhydrous potassium carbonate (8 mg) were placed in a 100 mL round-bottom flask and dissolved in 20 mL of carbon tetrachloride. The reaction apparatus was sealed, evacuated, and filled with nitrogen. The temperature was raised to 80 °C and the reaction was allowed to proceed for 8 h. After the reaction was completed, the organic phase was extracted with dichloromethane and water, and then purified by column chromatography with dichloromethane and petroleum ether (1:1) to obtain an orange-red solid of IrS2 with a yield of 24.1%. Figure 1 This is the single crystal structure diagram of the iridium complex IrS2 in this example.

[0062] 1 H NMR (400 MHz, CDCl3) δ 8.26 (s, 2H), 7.99 (s, 2H), 7.89 (s, 2H),7.83 (s, 2H), 7.71 (d, J = 3.4 Hz, 4H), 7.60 (s, 1H), 7.47 (d, J = 4.8 Hz, 2H),7.05 (s, 2H), 6.63 (s, 1H), 6.49 (s, 1H), 3.28 (s, 3H), 3.19 (s, 2H), 3.14(s, 2H), 2.97 (s, 3H), 2.91 (d, J = 7.7 Hz, 3H), 2.81 (s, 3H), 2.73 (d, J = 7.3Hz, 1H), 2.33 (s, 1H), 2.21 (d, J = 6.3 Hz, 1H), 1.35 (s, 3H), 1.34 (s, 3H), 1.32 (d, J = 4.1 Hz, 6H). 19 F NMR (376 MHz, CDCl3) δ -121.34 (d, J = 46.3 Hz, 3F),-122.61 (d, J = 23.2 Hz, 2F).

[0063] HRMS ((+)-ESI): m / z = 1097.3614 (calcd. 1097.3656 for [C 58 H 53 F5IrN2O2][M+H + ])

[0064] The reaction formula is as follows:

[0065]

[0066] The luminescence quantum efficiency of IrS2 in PMMA film is 54% when the mass percentage concentration is 1%. The UV-visible absorption spectrum and photoluminescence spectrum in dichloromethane solution are as follows: Figure 2 and Figure 3 shown.

[0067] Example 4

[0068] Ir1 (40 mg, 0.02 mmol), S1 (30 mg, 0.06 mmol), and 10 mg of anhydrous cesium carbonate were placed in a 100 mL round-bottom flask and dissolved in 30 mL of dichloromethane. The reaction apparatus was sealed, evacuated, and filled with nitrogen. The temperature was raised to 50 °C and the reaction was allowed to react for 6 h. After the reaction was completed, the organic phase was extracted with dichloromethane and water, and then purified by column chromatography with dichloromethane and petroleum ether (1:1) to obtain an orange-red solid of IrS3 with a yield of 25.6%.

[0069] NMR of the product: 1 H NMR (400 MHz, CDCl3) δ 8.80 (s, 3H), 8.13 (d, J = 8.3Hz, 3H), 7.64 (d, J = 1.5 Hz, 3H), 7.53 (t, J = 7.2 Hz, 6H), 7.45 (s, 3H),7.42 – 7.32 (m, 9H), 7.14 – 7.01 (m, 12H), 6.70 (d, J = 8.0 Hz, 6H), 6.07 (d,J = 7.9 Hz, 6H), 5.70 (s, 3H), 5.50 (s, 3H). 19 F NMR (377 MHz, CDCl3) δ -62.12 (s), -63.04 (s). Product mass spectrum: HRMS ((+)-ESI): m / z=1973.3984 (calcd. 1973.3987 for [C 108 H 57 F 18 IrN6][M+H] + ). The reaction formula is as follows:

[0070]

[0071] The luminescence quantum efficiency of IrS3 in PMMA film is 50% when the mass percentage concentration is 1%. The UV-visible absorption spectrum and photoluminescence spectrum in dichloromethane solution are as follows: Figure 2 and Figure 3shown.

[0072] Example 5

[0073] Ir2 (0.05 g, 0.03 mmol), 3 mL of triethylamine, and S1 (0.03 g, 0.07 mmol) were placed in a 100 mL round-bottom flask and dissolved in 20 mL of dichloromethane. The reaction apparatus was sealed, evacuated, and filled with nitrogen. The temperature was raised to 50°C and the reaction was allowed to proceed for 6 h. After the reaction was complete, the mixture was extracted with dichloromethane and water, and then purified on a silica gel column using a mixture of dichloromethane and petroleum ether (1:1) as the eluent. IrBS1 was obtained as a red solid in a 27.6% yield.

[0074] NMR of the product: 1 H NMR (400 MHz, CDCl3) δ 8.46 (s, 2H), 8.29 (s, 2H), 8.11 (s, 3H), 7.88 (d, J = 5.5 Hz, 1H), 7.62 (d, J = 8.7 Hz, 2H), 7.17 (d, J = 9.7 Hz,2H), 6.97 (d, J = 18.2 Hz, 2H), 6.85 (s, 1H), 6.70 (s, 2H), 6.36 (s, 1H), 5.83(s, 1H), 3.26 (s, 1H), 2.79 (s, 2H), 2.05 (d, J = 14.1 Hz, 2H), 1.75 (d, J = 13.3Hz, 2H), 1.62 (d, J = 11.3 Hz, 3H), 1.36 (d, J = 6.3 Hz, 3H), 1.19 (s, 3H), 1.17(s, 3H), 1.14 (d, J = 6.9 Hz, 6H). 19 F NMR (376 MHz, CDCl3) δ -62.75 (d, J = 10.9Hz, 3F).

[0075] Product mass spectrum: HRMS ((+)-ESI): m / z = 1569.2396 (calcd. 1569.2278 for [C 65 H 45 F 21IrN4O2S2] [M+H + ]). The reaction formula is as follows:

[0076]

[0077] The luminescence quantum efficiency of IrBS1 in PMMA film is 87% when the mass percentage concentration is 1%. The UV-visible absorption spectrum and photoluminescence spectrum in dichloromethane solution are shown in Figure 2. Figure 4 and Figure 5 shown.

[0078] Example 6

[0079] Ir2 (0.05 g, 0.03 mmol), 0.5 mL of di-n-butylamine, and S2 (0.04 g, 0.09 mmol) were placed in a 100 mL round-bottom flask and dissolved in 30 mL of chloroform. The reaction apparatus was sealed, evacuated, and filled with nitrogen. The temperature was raised to 70°C and the reaction was allowed to proceed for 4 h. After the reaction, the reaction was extracted with dichloromethane and water, and then purified on a silica gel column using a mixture of dichloromethane and petroleum ether (1:1) as the eluent. IrBS2 was obtained as a red solid in a 23.4% yield.

[0080] NMR of the product: 1 H NMR (400 MHz, CDCl3) δ 8.44 (s, 2H), 8.26 (s, 2H), 8.24(s, 2H), 7.92 (d, J = 5.4 Hz, 1H), 7.85 (d, J = 5.8 Hz, 1H), 7.69 (d, J = 8.5 Hz,2H), 7.20 (s, 2H), 7.04 (s, 2H), 6.90 (s, 2H), 6.84 (s, 1H), 6.77 (s, 1H),6.56 (s, 1H), 2.87 (s, 3H), 2.85 (s, 3H), 2.38 (s, 2H), 2.16 (d, J = 2.1 Hz, 2H), 1.76 (s, 2H), 1.69 (s, 1H), 1.28 (s, 3H), 1.26 (s, 3H), 1.24 (s, 3H), 1.22 (s, 3H). 19 F NMR (376 MHz, CDCl3) δ -62.72 (d, J = 2.0 Hz, 3F), -62.91 (d, J=3.4 Hz, 2F).

[0081] Product mass spectrum: HRMS ((+)-ESI): m / z = 1619.2246 (calcd. 1619.2246 for [C 66 H 45 F 23 IrN4O2S2] [M+H + ]). The reaction formula is as follows:

[0082]

[0083] The luminescence quantum efficiency of IrBS2 in PMMA film is 88% when the mass percentage concentration is 1%. The UV-visible absorption spectrum and photoluminescence spectrum in dichloromethane solution are as follows: Figure 4 and Figure 5 shown.

[0084] Example 7

[0085] Ir2 (0.05 g, 0.03 mmol), 1 mL of piperidine, and S3 (0.04 g, 0.08 mmol) were placed in a 100 mL round-bottom flask and dissolved in 20 mL of 1,2-dichloroethane. The reaction apparatus was sealed, evacuated, and filled with nitrogen. The temperature was raised to 90°C and the reaction was allowed to react for 2 h. After the reaction was complete, the mixture was extracted with dichloromethane and water, and then purified on a silica gel column using a mixture of dichloromethane and petroleum ether (1:1) as the eluent. IrBS3 was obtained as a red solid in a 27.4% yield.

[0086] NMR of the product: 1 H NMR (400 MHz, CDCl3) δ 8.43 (s, 2H), 8.27 (s, 2H), 8.16(d, J = 5.9 Hz, 2H), 8.12 (d, J = 1.1 Hz, 1H), 8.09 (s, 3H), 7.90 (d, J = 5.5 Hz,1H), 7.69 (d, J = 5.5 Hz, 2H), 6.95 (d, J = 11.0 Hz, 2H), 6.79 (s, 1H), 6.69 (s,1H), 6.34 (s, 1H), 5.97 (s, 1H), 2.85 (s, 1H), 2.72 (d, J= 21.1 Hz, 2H), 2.36(s, 2H), 2.22 (s, 2H), 2.01 (s, 3H), 1.77 (s, 3H), 1.33 (s, 3H), 1.28 (s,3H), 1.25 (s, 6H). 19 F NMR (376 MHz, CDCl3) δ -62.70 (s, 3F), -62.75 (s, 2F), -62.78 (s, 2F).

[0087] Product mass spectrum: HRMS ((+)-ESI): m / z = 1669.2202 (calcd. for 1669.2214[C 67 H 45 F 25 IrN4O2S2] [M+H + ]). The reaction formula is as follows:

[0088]

[0089] The luminescence quantum efficiency of IrBS3 in PMMA film is 60% when the mass percentage concentration is 1%. The UV-visible absorption spectrum and photoluminescence spectrum in dichloromethane solution are as follows: Figure 4 and Figure 5 shown.

[0090] Example 8

[0091] To demonstrate the electroluminescent properties of these iridium complexes, electroluminescent devices were fabricated. The iridium complexes prepared in this invention were co-evaporated with a host material to form an organic light-emitting diode (OLED). The device structure used in this experiment was ITO / MoO3 (3 nm) / NPB (40 nm) / TCTA (10 nm) / CBP:IrS2 (7% 20 nm) / TPBi (45 nm) / LiF (1 nm) / Al (100 nm).

[0092] The IrS2-based device has a turn-on voltage of 3.6 V and a maximum brightness of 7622 cd / m 2 The maximum power efficiency, current efficiency and external quantum efficiency are 24 lm w -1 ,27 cd A -1 , 12%. The asymmetry factor of the device is +2.0×10 -3 .

[0093] The method for manufacturing the organic light-emitting diode in the present invention is to use Fangsheng Optoelectronics' high-performance thermal evaporation coating device to vacuum-deposit the hole injection layer material, hole transport layer material, light-emitting layer material, electron transport layer material, and LiF / Al cathode on a tin-indium anode glass substrate in sequence.

[0094] It is worth noting that the reaction conditions in the above embodiments are all optimal reaction conditions for the reaction, and the reaction conditions within the scope of the claims can synthesize the complex of the present invention. In order to avoid redundancy, no further examples are given here. In addition, those skilled in the art can reproduce the present invention based on the general formula of the complex of the present invention and the related solvents, catalysts and other reagents listed. Since there are too many examples, several representative examples are selected here to prove that the complex of the present invention has excellent luminescence efficiency and low oxygen quenching rate, so the examples are not repeated here.

Claims

1. An iridium complex containing a rosin-based ligand, characterized in that: The general structural formula of the complex is as follows: ； In the formula, R1 is a fluoroalkyl group containing 1 to 8 carbon atoms, and the structural formula of R2 is or .

2. A method for preparing the iridium complex containing a rosin-based ligand according to claim 1, comprising the steps of: dissolving a chloro-bridged intermediate of the iridium complex and a rosin-based diketone ligand in an organic solvent, and subjecting the mixture to a dissociation reaction at 0-200° C. in the presence of a base for 1-24 hours to obtain the iridium complex containing a rosin-based ligand.

3. The method for preparing an iridium complex containing a rosin-based ligand according to claim 2, wherein: The iridium complex chlorine bridge intermediate is Ir1 or Ir2, and its structural formula is as follows: 。 4. The method for preparing an iridium complex containing a rosin-based ligand according to claim 2, wherein: The structural formula of the rosin-based diketone ligand is: 。 5. The method for preparing an iridium complex containing a rosin-based ligand according to claim 4, wherein: The preparation method of the rosin-based diketone ligand is as follows: NaH and a rosin-based derivative are mixed in an organic solvent, ice-bathed in a nitrogen environment for a period of time, and then a fluoroalkyl ester compound is added. The temperature is raised to 20-150° C. to obtain the rosin-based diketone ligand, wherein the rosin-based derivative has the structural formula: 。 6. The method for preparing an iridium complex containing a rosin-based ligand according to claim 2, wherein: The base is one or a mixture of two or more of sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, sodium hydride, sodium ethoxide, triethylamine, pyridine, dibutylamine, piperidine, and piperazine; the organic solvent is one or a mixture of two or more of dichloromethane, chloroform, 1,2-dichloroethane, carbon tetrachloride, o-dichlorobenzene, and toluene.

7. The method for preparing an iridium complex containing a rosin-based ligand according to claim 2, wherein: The molar fractions of each reactant in the reaction system are: 1 part of iridium complex chlorine bridge intermediate; 2-4 parts of rosin-based diketone ligand; 1-6 parts of alkali; 50-500 parts of organic solvent.

8. Use of the iridium complex containing a rosin-based ligand according to claim 1 as or in the preparation of a circularly polarized electroluminescent material.

9. Use of the iridium complex containing a rosin-based ligand according to claim 1 in the preparation of an organic circularly polarized light-emitting diode device.

10. An organic circularly polarized light-emitting diode device structure, comprising a cathode, an anode, and an organic thin film layer; The organic thin film layer is a light-emitting layer containing a light-emitting material and located between the cathode and the anode; The luminescent material used in the luminescent layer comprises the iridium complex containing the rosin-based ligand according to claim 1.

Images