CN102875542B - Oxadiazole group-containing red-light emitting iridium complex, and preparation method and use thereof - Google Patents

Abstract

Iridium red light complexes containing oxadiazole groups, they have the following structural formula: The iridium complexes of the present invention can be used in the light-emitting layer in electroluminescent devices. By modifying the phenyl group connected with oxazole, the solubility of the complex is improved, and it is possible to use it as a guest material for OLED. The invention discloses its preparation method.

Description

Red light iridium (Ш) complex containing oxadiazole group and its preparation method and application

field of invention

The invention relates to an iridium complex and an organic electroluminescence device.

Background technique

Organic Electroluminescence Devices (Organic Electroluminescence Devices or Organic Light-emitting Diodes, referred to as OLEDs), also known as light-emitting diodes, is a device in which voltage is applied to convert electrical energy into light energy. It is an ideal display screen for mobile phones and color TVs. Since 1987, Tang [referring to: Tang, C.W.; Vanslyke, S.A.Appl.Phys.Lett.1987,51,913] of American Kodak Company published the electroluminescence (EL ) devices, the research on electroluminescent materials and devices has aroused great interest in the world's scientific and technological circles and industries. EL devices are generally considered to be low energy consumption, wide viewing angle, and large-area flat panel display technology.

The unique advantages of OLEDs devices are closely related to the carrier transport materials, luminescent materials, electrode materials and device structures used in the devices. The luminescent materials are the core components of OLEDs devices, which can be divided into fluorescent materials and phosphorescent materials. Fluorescence arises from electronic transitions between homomultiple states with a maximum efficiency of only 25%. Since 1998, the Forrest group [see: Baldo, MA; O'Brien, DF; You, Y.; Shoustikov, A.; Sibley, S.; Thompson, ME; Forrest, SRNature 1998,395,151] reported that electrophosphorescent materials are due At the same time, singlet and triplet excitons can be harvested, so that the internal quantum efficiency of OLEDs has the potential to reach 100%, and the research on heavy metal electrophosphorescent materials is becoming more and more extensive [see: (a) Bolink, HJ; Cappelli, L.; Coronado, E.; M.; Ortí, E.; Costa, RD; Viruela, PM; Nazeeruddin, MK J Am. Chem. Soc. 2006, 128, 14786; (b) Wei, QH; Yin, GQ; .2006, 45, 10371]. Ir(III) transition metal complexes have attracted much attention due to their luminescence in solution at room temperature. They can be used as high-efficiency phosphors in OLEDs. Ir(III) complexes are the most studied class of phosphorescent materials due to their high quantum efficiency and short triplet lifetime. [See: (a) Lamansky, S.; Djurovich, P.; Murphy, D.; Abdel-Razzaq, F.; Lee, HE; Adachi, C.; Burrows, PE; Forrest, SR; .Soc.2001,123,4304.(b)Zhu,W.;Mo,Y.;Yuan,M.;Yang,W.;Cao,Y.Appl.Phys.Lett.2002,80,2045.]. Because of the heavy atom effect, these complexes can theoretically achieve 100% quantum efficiency and have unique photophysical and photochemical properties. They are good candidate materials for the light-emitting layer of OLEDs and have great research value.

However, many Ir(III) complexes reported in the literature for OLEDs are prone to triplet-inter-triplet and triplet-polaron annihilation, and the carrier transport properties of the materials have not reached the organic electroluminescent device OLEDs. requirements. Some studies have found that if the carrier transport group is introduced into the Ir(III) complex, its electron transport performance can be improved, thereby improving the performance of the device. [See: (a) Wong, W.-Y.; Ho, C.-L.; Gao, Z.-Q.; Mi, B.-X.; Chen, C.-H.; Cheah, K. -W.;Lin, Z.Y.Angew.Chem.Int.Ed.2006,45,7800.(b)Ding,J.Q.;Gao,J.;Cheng,Y.X.;Xie,Z.Y.;Wang,L.X.;Ma,D.G.;Jing ,X.B.;Wang,F.S.Adv.Funct.Mater.2006,16,575.(c)Ho,C.-L.;Wong,W.-Y.;Wang,Q.;Ma,D.G.;Wang,L.X.;Lin Z.Y. Adv. Funct. Mater. 2008, 18, 928.]

Contents of the invention

The present invention has designed 16 novel Ir(III) complexes containing oxadiazole groups, that is, introducing oxadiazole groups with better electron transport properties into phenylquinoline, and oxadiazole groups Modification is carried out to adjust the photoelectric properties of the complex in the molecule, so that it matches the energy level of the central ion Ir(III), and it can also improve the electron transport of the Ir(III) complex as a light-emitting layer material in OLEDs , increase the recombination probability of electrons and holes in the light-emitting layer, thereby improving the efficiency and brightness of the electroluminescent device.

Technical scheme of the present invention is as follows:

Ir(III) complexes containing oxadiazole groups, they have the following structural formula:

Wherein the definition of X ₁ , X ₂ , X ₃ , X ₄ and X ₅ is selected from one of the sixteen groups of R1-R16.

A method for preparing the above-mentioned iridium complex, which consists of the following steps:

Step 1, synthesis of ligand

Reaction of p-bromobenzoyl hydrazide and equimolar amounts of benzoyl chloride containing X ₁ , X ₂ , X ₃ , X ₄ and X ₅ substituents in chloroform at room temperature for dehydrochlorination, and then dehydration in POCl ₃ ring to obtain the corresponding brominated compound of the oxadiazole group containing X ₁ , X ₂ , X ₃ , X ₄ and X ₅ substituents. The ester reacts with n-butyllithium, and the corresponding boric acid is obtained after adding hydrochloric acid, and the boric acid and the equimolar amount of 2-chloroisoquinoline are catalyzed by 3% molar amount of tetrakis (triphenylphosphine) palladium.

The corresponding ligand L1-L16 is formed by Suzuki coupling reaction, and the structure of L1-L16 is as follows:

The definitions and substitution positions of X ₁ -X ₅ are the same as those of the above-mentioned iridium complexes;

Synthesis of step 2, Ir complex

Add iridium acetylacetonate (Ir(acac) ₃ ) in an anhydrous and oxygen-free nitrogen kettle, add 3 times the amount of iridium, one of the ligands L1-L16 and 5 times the amount of anthracene, and heat up to 300°C for reaction After 24 hours, dichloromethane and petroleum ether (volume ratio 2:1) were used as eluents and purified by column chromatography to obtain complexes R1-R16 respectively.

The iridium complexes of the present invention can be used as light-emitting materials in electroluminescent devices. After the complexes are introduced into oxazole groups with different modification groups on the phenylpyridine, the emission wavelength does not change greatly, but the luminescence is strong. There is a difference in strength and weakness, and they are all red light materials with better luminous performance.

Description of drawings

Figure 1: UV-Vis absorption spectra of complexes R1, R2, R3 and complex R16.

Figure 2: Emission spectra of complexes R1, R2, R3 and complex R16.

Detailed ways

Complexes of the present invention can be synthesized according to the following equation:

¹ H NMR, mass spectrometry, elemental analysis (C, H, N), infrared characterization and confirmed the structure of these iridium complexes, the instrument used for detection is Bruker DRX 500 nuclear magnetic resonance instrument, Perkin-Elmer240C elemental analyzer, Bruker Autoflex II TOF/TOF spectrometer mass spectrometer, UV-3100 ultraviolet-visible spectrophotometer and Hitachi F-4600 fluorometer.

Example 1: Preparation of ligands L1-L16 and corresponding iridium complexes G1-G16

1. Preparation of Ligands

In the reaction kettle, drop 100mL of 30mmol p-bromobenzoyl hydrazide in chloroform into 100mL of 30mmol benzoyl chloride in chloroform, stir for 2 hours, filter out the precipitate, dry it in the air, add 20mL POCl ₃ and 40mL The toluene was refluxed for 6 hours. The solvent was distilled off under reduced pressure, and recrystallized from a chloroform-methanol mixed solution. The crystallized product is 2-(4-bromobenzene)-5-phenyl-1,3,4-oxadiazole. Get 3.74mmol of 2-(4-bromobenzene)-5-phenyl-1,3,4-oxadiazole and dissolve it in anhydrous ether, and add 3.74mmol of n-butyllithium (2.4M n-hexane alkane solution), reacted overnight and slowly returned to room temperature. Then 10 mmol of hydrochloric acid was added dropwise in an ice-water bath to produce a white precipitate. After concentration by rotary evaporation, add methanol-petroleum ether for recrystallization to obtain 4-(5-phenyl-1,3,4-oxadiazole)phenylboronic acid. Take 1.56mmol 4-(5-phenyl-1,3,4-oxadiazole) phenylboronic acid, 1.56mmol 2-chloroisoquinoline, 15.6mmol sodium carbonate, 0.025mmol Pd(PPh ₃ ) ₄ , add 20mL methanol , 20mL of water, reacted at 100°C under nitrogen for 48 hours. After the reaction solution was concentrated, a large amount of water was added, extracted with ethyl acetate, the organic phase was washed with saturated brine, and dried over anhydrous sodium sulfate. Ethyl acetate and petroleum ether (volume ratio: 1:3) were used as eluents, and purified by column chromatography to obtain white solid L1. Yield: 80%.

Ligands L2-L16 were prepared using the corresponding substituted benzoyl chlorides and the same procedure as above. The ligand was verified by ¹ H NMR, elemental analysis, mass spectrometry, and infrared, and the results showed that the structure was correct. The data are as follows:

Ligand L1:

¹ H NMR (500MHz, CDCl ₃ )δ8.66(d,1H),8.34(d,2H),8.27-8.16(m,2H),8.12(d,1H),7.93(t,3H),7.75( dd,2H),7.67-7.54(m,4H).

Elemental analysis results: Calculated value: C(%): 79.07H(%): 4.33N(%): 12.03

Actual value: C(%): 79.05H(%): 4.34N(%): 12.04.

MS(ESI):m/z 350.013[M+H] ⁺

IR(KBr,cm ^-1 ):3054(C=CH),1610,1546,1493,1407(C=C,C=N,C=O),1358.

Ligand L2:

¹ H NMR (500MHz, CDCl ₃ )δ8.83(d,2H),8.42(d,1H),8.08-7.83(m,5H),7.70-7.32(m,6H),7.14(d,1H), 1.37(m,9H).

Elemental analysis results: Calculated value: C(%): 79.97H(%): 5.72N(%): 10.36

Actual value: C(%): 79.92H(%): 5.74N(%): 10.39

MS(ESI):m/z 406.51[M+H] ⁺

IR(KBr,cm ^-1 ):3056(C=CH),1615,1554,1498,1413(C=C,C=N,C=O),1362.

Ligand L3:

¹ H NMR (500MHz, CDCl ₃ )δ8.86(d,2H),8.45(d,1H),7.98-7.81(m,5H),7.69-7.34(m,8H),7.27(d,2H), 7.12(d,1H).

Elemental analysis results: Calculated value: C(%): 81.86H(%): 4.50N(%): 9.88

Actual value: C(%): 81.80H(%): 4.53N(%): 9.94

MS(ESI):m/z 426.53[M+H] ⁺

IR(KBr,cm ^-1 ):3050(C=CH),1603,1539,1487,1402(C=C,C=N,C=O),1351.

Ligand L4:

¹ H NMR (500MHz, CDCl ₃ )δ8.79(d,2H),8.38(d,1H),7.94-7.77(m,7H),7.60-7.32(m,3H),7.06(d,1H).

Elemental analysis results: Calculated value: C(%): 76.99H(%): 3.77N(%): 14.96

Actual value: C(%): 76.93H(%): 3.79N(%): 15.00

MS(ESI):m/z 375.35[M+H] ⁺

IR(KBr,cm ^-1 ):3049(C=CH),1600,1541,1488,1400(C=C,C=N,C=O),1356.

Ligand L5:

¹ H NMR (500MHz, CDCl ₃ ) δ8.85(d, 2H), 8.46(d, 1H), 7.97-7.81(m, 3H), 7.67-7.24(m, 5H), 7.12(d, 1H).

Elemental analysis results: Calculated value: C(%): 75.19H(%): 3.84N(%): 11.44

Actual value: C(%): 75.15H(%): 3.86N(%): 11.47

MS(ESI):m/z 368.41[M+H] ⁺

IR(KBr,cm ^-1 ):3061(C=CH),1623,1556,1503,1416(C=C,C=N,C=O),1362.

Ligand L6:

¹ H NMR (500MHz, CDCl ₃ )δ8.82(d,2H),8.47(d,1H),8.06-7.82(m,5H),7.75-7.57(m,3H),7.53-7.38(m,2H ), 7.14(d, 1H).

Elemental analysis results: Calculated value: C(%): 69.06H(%): 3.38N(%): 10.07

Actual value: C(%): 69.02H(%): 3.39N(%): 10.09

MS(ESI):m/z 418.39[M+H] ⁺

IR(KBr,cm ^-1 ):3054(C=CH),1613,1548,1494,1411(C=C,C=N,C=O),1361.

Ligand L7:

¹ H NMR (500MHz, CDCl ₃ )δ8.79(d,2H),8.38(d,1H),8.09-7.80(m,5H),7.66-7.37(m,3H),7.15-7.00(m,3H ).

Elemental analysis results: Calculated value: C(%): 66.51H(%): 3.26N(%): 9.70

Actual value: C(%): 66.47H(%): 3.28N(%): 9.73

MS(ESI):m/z 434.42[M+H] ⁺

IR(KBr,cm ^-1 ):3051(C=CH),1604,1542,1487,1401(C=C,C=N,C=O),1353.

Ligand L8:

¹ H NMR (500MHz, CDCl ₃ )δ8.83(d,2H),8.44(d,1H),8.04-7.69(m,4H),7.69-7.38(m,3H),7.17-7.02(m,2H ),6.75(t,1H).

Elemental analysis results: Calculated value: C(%): 71.68H(%): 3.40N(%): 10.90

Actual value: C(%): 71.64H(%): 3.41N(%): 10.92

MS(ESI):m/z 386.33[M+H] ⁺

IR(KBr,cm ^-1 ):3048(C=CH),1602,1543,1487,1404(C=C,C=N,C=O),1354.

Ligand L9:

¹ H NMR (500MHz, CDCl ₃ )δ8.80(d,2H),8.41(d,1H),8.03-7.82(m,3H),7.67-7.22(m,5H),7.12(d,1H), 6.65(t,1H).

Elemental analysis results: Calculated value: C(%): 71.68H(%): 3.40N(%): 10.90

Actual value: C(%): 71.65H(%): 3.42N(%): 10.93

MS(ESI):m/z 386.34[M+H] ⁺

IR(KBr,cm ^-1 ):3057(C=CH),1621,1551,1498,1416(C=C,C=N,C=O),1364.

Ligand L10:

¹ H NMR (500MHz, CDCl ₃ ) δ8.85(d,2H),8.46(d,1H),8.08-7.85(m,4H),7.75-7.58(m,3H),7.56-7.45(m,2H ),7.18(d,1H).

Elemental analysis results: Calculated value: C(%): 61.86H(%): 2.70N(%): 8.66

Actual value: C(%): 61.81H(%): 2.73N(%): 8.69

MS(ESI):m/z 486.42[M+H] ⁺

IR(KBr,cm ^-1 ):3061(C=CH),1623,1557,1501,1419(C=C,C=N,C=O),1365.

Ligand L11:

¹ H NMR (500MHz, CDCl ₃ )δ8.84(d,2H),8.43(d,1H),8.04-7.81(m,3H),7.73-7.56(m,2H),7.54-7.35(m,3H ),7.28-7.04(m,2H).

Elemental analysis results: Calculated value: C(%): 66.21H(%): 3.01N(%): 9.65

Actual value: C(%): 66.17H(%): 3.03N(%): 9.67

MS(ESI):m/z 436.42[M+H] ⁺

IR(KBr,cm ^-1 ):3049(C=CH),1601,1540,1489,1398(C=C,C=N,C=O),1349.

Ligand L12:

¹ H NMR (500MHz, CDCl ₃ )δ8.88(d,2H),8.45(d,1H),8.06-7.84(m,3H),7.69-7.32(m,4H),7.18-7.01(m,2H ).

Elemental analysis results: Calculated value: C(%): 68.49H(%): 3.00N(%): 10.42

Actual value: C(%): 68.45H(%): 3.03N(%): 10.46

MS(ESI):m/z 404.37[M+H] ⁺

IR(KBr,cm ^-1 ):3051(C=CH),1607,1542,1487,1402(C=C,C=N,C=O),1353.

Ligand L13:

¹ H NMR (500MHz, CDCl ₃ )δ8.91(d,2H),8.48(d,1H),8.11-7.87(m,3H),7.73-7.36(m,3H),7.28(m,2H), 7.14(d,1H).

Elemental analysis results: Calculated value: C(%): 68.49H(%): 3.00N(%): 10.42

Actual value: C(%): 68.44H(%): 3.02N(%): 10.45

MS(ESI):m/z 404.37[M+H] ⁺

IR(KBr,cm ^-1 ):3048(C=CH),1600,1538,1486,1400(C=C,C=N,C=O),1351.

Ligand L14:

¹ H NMR (500MHz, CDCl ₃ )δ8.82(d,2H),8.40(d,1H),8.02-7.81(m,3H),7.65-7.336(m,3H),7.22(m,1H), 6.97(d,1H).

Elemental analysis results: Calculated value: C(%): 65.56H(%): 2.63N(%): 9.97

Actual value: C(%): 65.53H(%): 2.64N(%): 9.99

MS(ESI):m/z 422.37[M+H] ⁺

IR(KBr,cm ^-1 ):3059(C=CH),1617,1552,1499,1414(C=C,C=N,C=O),1363.

Ligand L15:

¹ H NMR (500MHz, CDCl ₃ )δ8.85(d,2H),8.43(d,1H),8.04-7.83(m,3H),7.68-7.30(m,3H),7.06(d,1H), 6.58(m,1H).

Elemental analysis results: Calculated value: C(%): 65.56H(%): 2.63N(%): 9.97

Actual value: C(%): 65.52H(%): 2.65N(%): 8.01

MS(ESI):m/z 422.37[M+H] ⁺

IR(KBr,cm ^-1 ):3059(C=CH),1617,1552,1499,1414(C=C,C=N,C=O),1363.

Ligand L16:

¹ H NMR (500MHz, CDCl ₃ )δ8.89(d,2H),8.48(d,1H),8.08-7.89(m,3H),7.71-7.39(m,3H),7.15(d,1H).

Elemental analysis results: Calculated value: C(%): 62.88H(%): 2.29N(%): 9.56

Actual value: C(%): 62.84H(%): 2.31N(%): 9.58

MS(ESI):m/z 440.36[M+H] ⁺

IR(KBr,cm ^-1 ):3059(C=CH),1626,1553,1507,1421(C=C,C=N,C=O),1369.

2. Preparation of R1-R16

Add Ir(acac) ₃ , one of the ligands L1-L16 and 5 times the amount of anthracene in an anhydrous and oxygen-free nitrogen kettle, raise the temperature to 300°C for 24 hours, dichloromethane and petroleum ether (Volume ratio 2:1) as the eluent, the complexes R1-R16 can be obtained by column chromatography purification.

The compound was verified by ¹ H NMR, elemental analysis, and mass spectrometry, and the results showed that the structure was correct. The data are as follows:

Complex R1:

¹ H NMR (500MHz, CDCl ₃ )δ9.03(d,3H),8.46(d,3H),8.07(d,3H),7.83(d,9H),7.76(p,6H),7.64(d, 3H), 7.52-7.45(m, 9H), 7.43(d, 3H), 7.32(d, 3H).

Elemental analysis results: Calculated value: C(%): 66.98H(%): 3.42N(%): 10.19

Actual value: C(%): 67.01H(%): 3.43N(%): 10.15

MS(MALDI-TOF):m/z1236.67(M ⁺ )

Complex R2:

¹ H NMR (500MHz, CDCl ₃ )δ9.01(d,3H),8.43(d,3H),8.05(d,6H),7.82(m,6H),7.66-7.35(m,6H),7.64( d,3H),7.52-7.45(m,9H),7.43(d,3H),7.32(d,3H),1.35(s,9H).

Elemental analysis results: Calculated value: C(%): 69.21H(%): 4.73N(%): 8.97

Actual value: C(%): 69.18H(%): 4.75N(%): 8.99

MS(MALDI-TOF):m/z1404.68(M ⁺ )

Complex R3:

¹ H NMR (500MHz, CDCl ₃ )δ9.05(d,3H),8.98(d,3H),8.03-7.80(m,12H),7.69-7.55(m,6H),7.64(d,3H), 7.59-7.40(m,21H),7.28(d,6H),7.02(d,3H).

Elemental analysis results: Calculated value: C(%): 71.30H(%): 3.71N(%): 8.60

Actual value: C(%): 71.24H(%): 3.73N(%): 8.64

MS(MALDI-TOF):m/z1464.64(M ⁺ )

Complex R4:

¹ H NMR (500MHz, CDCl ₃ )δ9.12(d,3H),8.97(d,3H),8.09-7.73(m,18H),7.65-7.53(m,6H),7.55-7.47(m,6H ),7.06(d,3H).

Elemental analysis results: Calculated value: C(%): 65.89H(%): 3.00N(%): 12.81

Actual value: C(%): 65.83H(%): 3.05N(%): 12.84

MS(MALDI-TOF):m/z1311.27(M ⁺ )

Complex R5:

¹ H NMR (500MHz, CDCl ₃ )δ9.16(d,3H),8.99(d,3H),8.87(t,6H),7.97-7.81(m,6H),7.69-7.55(m,6H), 7.58-7.42(m,6H),7.31(t,6H),7.02(d,3H).

Elemental analysis results: Calculated value: C(%): 64.18H(%): 3.04N(%): 9.76

Actual value: C(%): 64.14H(%): 3.06N(%): 9.78

MS(MALDI-TOF):m/z1290.35(M ⁺ )

Complex R6:

¹ H NMR (500MHz, CDCl ₃ )δ9.11(d,3H),8.82(d,3H),8.61(t,6H),7.95-7.84(m,6H),7.74-7.53(m,12H), 7.54-7.38(m,6H),7.06(d,3H).

Elemental analysis results: Calculated value: C(%): 60.00H(%): 2.73N(%): 8.75

Actual value: C(%): 59.94H(%): 2.75N(%): 8.78

MS(MALDI-TOF):m/z1440.36(M ⁺ )

Complex R7:

¹ H NMR (500MHz, CDCl ₃ )δ9.02(d,3H),8.80(d,3H),8.12(t,6H),7.98-7.83(m,6H),7.69-7.54(m,6H), 7.57-7.35(m,6H),7.17-6.97(m,6H).

Elemental analysis results: Calculated value: C(%): 58.06H(%): 2.64N(%): 8.46

Actual value: C(%): 58.07H(%): 2.65N(%): 8.49

MS(MALDI-TOF):m/z1488.37(M ⁺ )

Complex R8:

¹ H NMR (500MHz, CDCl ₃ )δ9.00(d,3H),8.77(d,3H),8.12(t,6H),7.95-7.81(m,6H),7.76(p,3H),7.65- 7.48(m,6H),7.54-7.32(m,6H),7.17-7.01(m,6H),6.73(p,3H).

Elemental analysis results: Calculated value: C(%): 61.60H(%): 2.70N(%): 9.37

Actual value: C(%): 61.56H(%): 2.72N(%): 9.38

MS(MALDI-TOF):m/z1344.27(M ⁺ )

Complex R9:

¹ H NMR (500MHz, CDCl ₃ ) δ9.05(d,3H),8.85(d,3H),8.03-7.85(m,6H),7.70-7.60(m,6H),7.53-7.36(m,6H ),7.27(d,6H),7.13(d,3H),6.61(m,3H).

Elemental analysis results: Calculated value: C(%): 61.60H(%): 2.70N(%): 9.37

Actual value: C(%): 61.58H(%): 2.71N(%): 9.39

MS(MALDI-TOF):m/z1344.27(M ⁺ )

Complex R10:

¹ H NMR (500MHz, CDCl ₃ ) δ9.11(d,3H),8.91(d,3H),8.08-7.93(m,9H),7.77-7.65(m,9H),7.55-7.38(m,6H ),7.27(d,6H),7.16(d,3H).

Elemental analysis results: Calculated value: C(%): 54.75H(%): 2.21N(%): 7.66

Actual value: C(%): 54.73H(%): 2.22N(%): 7.68

MS(MALDI-TOF):m/z1644.35(M ⁺ )

Complex R11:

¹ H NMR (500MHz, CDCl ₃ )δ9.03(d,3H),8.87(d,3H),8.03-7.88(m,6H),7.73(t,9H),7.64-7.57(m,6H), 7.52-7.31(m,9H),7.21(d,3H),7.07(d,3H).

Elemental analysis results: Calculated value: C(%): 57.83H(%): 2.43N(%): 8.43

Actual value: C(%): 57.78H(%): 2.44N(%): 8.46

MS(MALDI-TOF):m/z1494.32(M ⁺ )

Complex R12:

¹ H NMR (500MHz, CDCl ₃ )δ8.97(d,3H),8.82(d,3H),7.93-7.81(m,6H),7.63-7.57(m,6H),7.52-7.31(m,9H ),7.11-7.00(m,6H).

Elemental analysis results: Calculated value: C(%): 59.23H(%): 2.38N(%): 9.01

Actual value: C(%): 59.20H(%): 2.40N(%): 9.03

MS(MALDI-TOF):m/z1398.31(M ⁺ )

Complex R13:

¹ H NMR (500MHz, CDCl ₃ )δ9.03(d,3H),8.88(d,3H),7.96-7.87(m,6H),7.66-7.59(m,6H),7.57-7.40(m,6H ),7.29(t,6H),7.15(d,3H).

Elemental analysis results: Calculated value: C(%): 59.23H(%): 2.38N(%): 9.01

Actual value: C(%): 59.21H(%): 2.39N(%): 9.03

MS(MALDI-TOF):m/z1398.32(M ⁺ )

Complex R14:

¹ H NMR (500MHz, CDCl ₃ ) δ9.00(d,3H),8.84(d,3H),7.92-7.83(m,6H),7.66-7.59(m,6H),7.57-7.40(m,6H ), 7.22(p,3H), 7.09(d,3H).

Elemental analysis results: Calculated value: C(%): 57.03H(%): 2.08N(%): 8.67

Actual value: C(%): 57.00H(%): 2.09N(%): 8.68

MS(MALDI-TOF):m/z1453.22(M ⁺ )

Complex R15:

¹ H NMR (500MHz, CDCl ₃ )δ8.98(d,3H),8.81(d,3H),7.90-7.81(m,6H),7.62-7.57(m,6H),7.57-7.40(m,6H ),7.08(d,3H),6.61(m,3H).

Elemental analysis results: Calculated value: C(%): 57.03H(%): 2.08N(%): 8.67

Actual value: C(%): 57.01H(%): 2.10N(%): 8.69

MS(MALDI-TOF):m/z1453.23(M ⁺ )

Complex R16:

¹ H NMR (500MHz, CDCl ₃ )δ8.96(d,3H),8.78(d,3H),7.87-7.79(m,6H),7.60-7.54(m,6H),7.50-7.38(m,6H ),7.01(d,3H).

Elemental analysis results: Calculated value: C(%): 54.99H(%): 1.81N(%): 8.36

Actual value: C(%): 54.95H(%): 1.83N(%): 8.38

MS(MALDI-TOF):m/z1507.18(M ⁺ )

Example 2: Fluorescence characterization of complexes of the present invention

The test instrument is a Hitachi F4600 fluorescence instrument, and the above-mentioned iridium complex is dissolved in dichloromethane (10 ^-5 M) for measurement. At room temperature, the emission peak positions are respectively:

Complex R1:

λ _em,max ,nm 633 (see Figure 2);

Complex R2

λ _em,max ,nm 633 (see Figure 2);

Complex 3

λ _em,max ,nm 647 (see Figure 2);

Complex R16

λ _{em, max} , nm 613 (see Figure 2).

Claims (3)

1., containing Ir (III) title complex of oxadiazole group, it is characterized in that they have following structural formula:

Wherein X ₁, X ₂, X ₃, X ₄and X ₅one of definition 16 groups that are selected from R1-R16.

2. prepare a method for complex of iridium according to claim 1, it is characterized in that it comprises the following steps:

The synthesis of step 1, part

By to bromobenzoylhydrazine and equimolar amount containing X ₁, X ₂, X ₃, X ₄and X ₅substituent Benzoyl chloride reacts dehydrochlorination under room temperature in chloroform, then at POCl ₃middle dehydration ring closure obtains corresponding to X ₁, X ₂, X ₃, X ₄and X ₅the bromo compound of the oxadiazole group of substituting group, gained bromo compound under liquid nitrogen cryogenics again by reacting with the trimethyl borate and n-Butyl Lithium of equimolar amount, corresponding boric acid is obtained after adding hydrochloric acid, the structure that Suzuki linked reaction forms respective ligand L1-L16, L1-L16 occurs under the tetrakis triphenylphosphine palladium catalysis of 3% molar weight for the boric acid of gained and the 2-chlorine isoquinoline 99.9 of equimolar amount is as follows:

Described X ₁-X ₅definition and the position of substitution with above-mentioned complex of iridium;

The synthesis of step 2, Ir title complex

Methyl ethyl diketone iridium (Ir (acac) is added in the nitrogen still of anhydrous and oxygen-free ₃), add one and the 5 times amount anthracenes of 3 times amount ligand L 1-L16 of the amount of substance of iridium, be warming up to 300 DEG C reaction 24 hours, volume ratio be the dichloromethane-petroleum ether of 2 ﹕ 1 as eluent, by column chromatography purify can obtain title complex R1-R16 respectively.

3. the title complex of iridium according to claim 1 is preparing the application in electroluminescent device.