CN102875542B - Oxadiazole group-containing red-light emitting iridium complex, and preparation method and use thereof - Google Patents
Oxadiazole group-containing red-light emitting iridium complex, and preparation method and use thereof Download PDFInfo
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 16
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 16
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000010668 complexation reaction Methods 0.000 title 1
- 239000003446 ligand Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- -1 bromo compound Chemical class 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- HGONAVGTQFIEEU-UHFFFAOYSA-N N-bromobenzohydrazide Chemical compound BrN(N)C(C1=CC=CC=C1)=O HGONAVGTQFIEEU-UHFFFAOYSA-N 0.000 claims description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001454 anthracenes Chemical class 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- RCKMYZVXXQPSNC-UHFFFAOYSA-N [Ir].C(C)C(=O)C(=O)C Chemical compound [Ir].C(C)C(=O)C(=O)C RCKMYZVXXQPSNC-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 32
- 238000000921 elemental analysis Methods 0.000 description 32
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The invention discloses an oxadiazole group-containing red-light emitting iridium complex which has a structural formula shown in the specifications. The iridium complex can be used as a luminous layer in an electroluminescent device. Phenyl connected with oxazole is modified, the solubility of the complex is improved, and the complex is possibly used as an object material of an organic light emitting diode (OLED). The invention discloses a preparation method for the complex.
Description
Invention field
The present invention relates to complex of iridium and organic electroluminescence device.
Background technology
Organic electroluminescence device (Organic Electroluminescence Devices or Organic Light-emitting Diodes, be called for short OLEDs), also known as photodiode, being apply voltage wherein and be the device of luminous energy by electric energy conversion, is the display screens such as desirable mobile phone, colour TV.From the Tang of Kodak in 1987 [see Tang, C.W.; Vanslyke, S.A.Appl.Phys.Lett.1987,51,913] since having delivered the double-deck electroluminescent of small molecules organic film (EL) device of the efficient high brightness of low voltage starting, the research of electroluminescent material and device causes the great interest of world technology circle and industry member, and El element is generally considered and can has less energy-consumption, wide viewing angle, large-area flat panel display simultaneously concurrently.
The structure of carrier transmission material, luminescent material, electrode materials and device that the particular advantages of OLEDs device and device adopt has relation closely, and wherein luminescent material is the core component of OLEDs device, can be divided into fluorescent material and phosphor material two kinds.Fluorescence results from the transition of electron between multiplicity of the same race, and maximum efficiency only has 25%.From Forrest group in 1998 [see Baldo, M.A.; O ' Brien, D.F.; You, Y.; Shoustikov, A.; Sibley, S.; Thompson, M.E.; Forrest; S.R.Nature 1998; 395; 151] report that electromechanical phosphorescent material is owing to can gather in the crops singlet state and triplet exciton simultaneously; the internal quantum efficiency of OLEDs is had reach 100% potential may; the research of heavy metal electromechanical phosphorescent material is increasingly extensive [see (a) Bolink, H.J.; Cappelli, L.; Coronado, E.;
m.; Ort í, E.; Costa, R.D.; Viruela, P.M.; Nazeeruddin, M.K.J.Am.Chem.Soc.2006,128,14786; (b) Wei, Q.H.; Yin, G.Q.; Zhang, L.Y.; Chen, Z.N.Inorg.Chem.2006,45,10371].Ir (III) transition metal complex receives much concern owing to can produce luminescence phenomenon in solution at room temperature.They can be used as efficient phosphorescent substance in OLED, the quantum yield higher due to Ir (III) title complex and shorter triplet lifetime, so Ir title complex is a class phosphor material of current most study.[see: (a) Lamansky, S.; Djurovich, P.; Murphy, D.; Abdel-Razzaq, F.; Lee, H.E.; Adachi, C.; Burrows, P.E.; Forrest, S.R.; Thompson, M.E.J.Am.Chem.Soc.2001,123,4304. (b) Zhu, W.; Mo, Y.; Yuan, M.; Yang, W.; Cao, Y.Appl.Phys.Lett.2002,80,2045.].Owing to there is heavy atoms effect in this kind of title complex, quantum yield can reach 100% in theory, has unique optical physics, spectrochemical property, be the good candidate materials of OLEDs luminescent layer, have very large researching value.
But the Ir for OLEDs (III) title complex of a lot of bibliographical information easily occurs to bury in oblivion between triplet state-triplet state and between triplet state-polaron, and the carrier transmission performance of material does not reach the requirement of organic electroluminescent device OLED s yet.Part studies discovery, if introduce carrier transport group can improve its electronic transmission performance in Ir (III) title complex, thus improves the performance of 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.]
Summary of the invention
The present invention devises 16 novel Ir (III) title complexs containing oxadiazole group, namely in phenylquinoline, introduce the oxadiazole group with better electronic transmission performance; and oxadiazole group is modified, regulate and control in the photoelectric properties of intramolecule to title complex, itself and central ion Ir (III) energy level are matched, also can improve Ir (III) title complex as the electron-transporting of emitting layer material in OLEDs simultaneously, increase electronics and the recombination probability of hole in luminescent layer, thus the performance such as the efficiency of raising electroluminescent device and brightness.
Technical scheme of the present invention is as follows:
Containing Ir (III) title complex of oxadiazole group, 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.
Prepare a method for above-mentioned complex of iridium, it is made up of the following step:
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, obtain corresponding boric acid after adding hydrochloric acid, the boric acid of gained and the 2-chlorine isoquinoline 99.9 of equimolar amount issue in the tetrakis triphenylphosphine palladium catalysis of 3% molar weight
The structure that raw Suzuki linked reaction forms respective ligand L1-L16, L1-L16 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 of reactions 24 hours, methylene dichloride and sherwood oil (volume ratio 2:1), as eluent, are purified can be obtained title complex R1-R16 respectively by column chromatographies.
Complex of iridium in the present invention can be used for the luminescent material in electroluminescent device, after title complex introduces the oxazole group with different modifying group on phenylpyridine, emission wavelength does not have large change, and just luminous intensity has strong and weak other, is all the good red light material of luminescent properties.
Accompanying drawing explanation
Fig. 1: the uv-visible absorption spectra of title complex R1, R2, R3 and title complex R16.
Fig. 2: the emmission spectrum spectrum of title complex R1, R2, R3 and title complex R16.
Embodiment
Title complex of the present invention can synthesize according to following equation:
With
1h NMR, mass spectrum, ultimate analysis (C, H, N), Infrared Characterization confirm the structure of the title complex of these iridium, detecting instrument is Bruker DRX 500 type nuclear magnetic resonance analyser, Perkin-Elmer240C type elemental analyser, Bruker Autoflex II TOF/TOF spectrometer mass spectrometer, UV-3100 ultraviolet-visible spectrophotometer and Hitachi F-4600 luminoscope.
The preparation of embodiment one: ligand L 1-L16 and corresponding complex of iridium G1-G16
1. the preparation of part
In a kettle., be added drop-wise in the chloroformic solution of 100mL30mmol Benzoyl chloride by the chloroformic solution 100mL of 30mmol to bromobenzoylhydrazine, stirring reaction 2 hours, filters out precipitation, adds 20mL POCl in air after drying
3with 40mL refluxing toluene 6 hours.Underpressure distillation removes desolventizing, with chloroform-methanol mixing solutions recrystallization.Crystallized product is 2-(4-bromobenzene)-5-phenyl-1,3,4-oxadiazole.Getting 2-(4-bromobenzene)-5-phenyl-1,3,4-oxadiazole 3.74mmol is dissolved in anhydrous diethyl ether, and drip the n-Butyl Lithium (2.4M hexane solution) of 3.74mmol under low temperature nitrogen atmosphere, reaction is spent the night, and slowly returns to room temperature.Then in ice-water bath, drip the hydrochloric acid of 10mmol, produce white precipitate.Add methyl alcohol-sherwood oil recrystallization after concentrated by rotary evaporation and obtain 4-(5-phenyl-1,3,4-oxadiazole) phenylo boric acid.Get 1.56mmol 4-(5-phenyl-1,3,4-oxadiazole) phenylo boric acid, 1.56mmol 2-chlorine isoquinoline 99.9,15.6mmol sodium carbonate, 0.025mmol Pd (PPh
3)
4, add 20mL methyl alcohol, 20mL water, react 48 hours under 100 DEG C of condition of nitrogen gas.Large water gaging is added, extraction into ethyl acetate, saturated common salt water washing organic phase, anhydrous sodium sulfate drying after reaction solution is concentrated.Do elutriant with ethyl acetate and sherwood oil (volume ratio is 1:3), column chromatography is purified, and obtains white solid L1.Productive rate: 80%.
Ligand L 2-L16 is obtained with identical aforesaid method with corresponding substituted benzoyl chloride.Part warp
1h NMR, ultimate analysis, mass spectrum, infraredly to verify, result shows that structure is correct, and data are as follows:
Ligand L 1:
1H 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).
Results of elemental analyses: calculated value: C (%): 79.07H (%): 4.33N (%): 12.03
Measured value: C (%): 79.05H (%): 4.34N (%): 12.04.
MS(ESI):m/z 350.013[M+H]
+
IR(KBr,cm
-1):3054(C=C-H),1610,1546,1493,1407(C=C,C=N,C=O),1358.
Ligand L 2:
1H 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).
Results of elemental analyses: calculated value: C (%): 79.97H (%): 5.72N (%): 10.36
Measured value: C (%): 79.92H (%): 5.74N (%): 10.39
MS(ESI):m/z 406.51[M+H]
+
IR(KBr,cm
-1):3056(C=C-H),1615,1554,1498,1413(C=C,C=N,C=O),1362.
Ligand L 3:
1H 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).
Results of elemental analyses: calculated value: C (%): 81.86H (%): 4.50N (%): 9.88
Measured value: C (%): 81.80H (%): 4.53N (%): 9.94
MS(ESI):m/z 426.53[M+H]
+
IR(KBr,cm
-1):3050(C=C-H),1603,1539,1487,1402(C=C,C=N,C=O),1351.
Ligand L 4:
1H 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).
Results of elemental analyses: calculated value: C (%): 76.99H (%): 3.77N (%): 14.96
Measured value: C (%): 76.93H (%): 3.79N (%): 15.00
MS(ESI):m/z 375.35[M+H]
+
IR(KBr,cm
-1):3049(C=C-H),1600,1541,1488,1400(C=C,C=N,C=O),1356.
Ligand L 5:
1H 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).
Results of elemental analyses: calculated value: C (%): 75.19H (%): 3.84N (%): 11.44
Measured value: C (%): 75.15H (%): 3.86N (%): 11.47
MS(ESI):m/z 368.41[M+H]
+
IR(KBr,cm
-1):3061(C=C-H),1623,1556,1503,1416(C=C,C=N,C=O),1362.
Ligand L 6:
1H 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).
Results of elemental analyses: calculated value: C (%): 69.06H (%): 3.38N (%): 10.07
Measured value: C (%): 69.02H (%): 3.39N (%): 10.09
MS(ESI):m/z 418.39[M+H]
+
IR(KBr,cm
-1):3054(C=C-H),1613,1548,1494,1411(C=C,C=N,C=O),1361.
Ligand L 7:
1H 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).
Results of elemental analyses: calculated value: C (%): 66.51H (%): 3.26N (%): 9.70
Measured value: C (%): 66.47H (%): 3.28N (%): 9.73
MS(ESI):m/z 434.42[M+H]
+
IR(KBr,cm
-1):3051(C=C-H),1604,1542,1487,1401(C=C,C=N,C=O),1353.
Ligand L 8:
1H 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).
Results of elemental analyses: calculated value: C (%): 71.68H (%): 3.40N (%): 10.90
Measured value: C (%): 71.64H (%): 3.41N (%): 10.92
MS(ESI):m/z 386.33[M+H]
+
IR(KBr,cm
-1):3048(C=C-H),1602,1543,1487,1404(C=C,C=N,C=O),1354.
Ligand L 9:
1H 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).
Results of elemental analyses: calculated value: C (%): 71.68H (%): 3.40N (%): 10.90
Measured value: C (%): 71.65H (%): 3.42N (%): 10.93
MS(ESI):m/z 386.34[M+H]
+
IR(KBr,cm
-1):3057(C=C-H),1621,1551,1498,1416(C=C,C=N,C=O),1364.
Ligand L 10:
1H 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).
Results of elemental analyses: calculated value: C (%): 61.86H (%): 2.70N (%): 8.66
Measured value: C (%): 61.81H (%): 2.73N (%): 8.69
MS(ESI):m/z 486.42[M+H]
+
IR(KBr,cm
-1):3061(C=C-H),1623,1557,1501,1419(C=C,C=N,C=O),1365.
Ligand L 11:
1H 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).
Results of elemental analyses: calculated value: C (%): 66.21H (%): 3.01N (%): 9.65
Measured value: C (%): 66.17H (%): 3.03N (%): 9.67
MS(ESI):m/z 436.42[M+H]
+
IR(KBr,cm
-1):3049(C=C-H),1601,1540,1489,1398(C=C,C=N,C=O),1349.
Ligand L 12:
1H 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).
Results of elemental analyses: calculated value: C (%): 68.49H (%): 3.00N (%): 10.42
Measured value: C (%): 68.45H (%): 3.03N (%): 10.46
MS(ESI):m/z 404.37[M+H]
+
IR(KBr,cm
-1):3051(C=C-H),1607,1542,1487,1402(C=C,C=N,C=O),1353.
Ligand L 13:
1H 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).
Results of elemental analyses: calculated value: C (%): 68.49H (%): 3.00N (%): 10.42
Measured value: C (%): 68.44H (%): 3.02N (%): 10.45
MS(ESI):m/z 404.37[M+H]
+
IR(KBr,cm
-1):3048(C=C-H),1600,1538,1486,1400(C=C,C=N,C=O),1351.
Ligand L 14:
1H 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).
Results of elemental analyses: calculated value: C (%): 65.56H (%): 2.63N (%): 9.97
Measured value: C (%): 65.53H (%): 2.64N (%): 9.99
MS(ESI):m/z 422.37[M+H]
+
IR(KBr,cm
-1):3059(C=C-H),1617,1552,1499,1414(C=C,C=N,C=O),1363.
Ligand L 15:
1H 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).
Results of elemental analyses: calculated value: C (%): 65.56H (%): 2.63N (%): 9.97
Measured value: C (%): 65.52H (%): 2.65N (%): 8.01
MS(ESI):m/z 422.37[M+H]
+
IR(KBr,cm
-1):3059(C=C-H),1617,1552,1499,1414(C=C,C=N,C=O),1363.
Ligand L 16:
1H 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).
Results of elemental analyses: calculated value: C (%): 62.88H (%): 2.29N (%): 9.56
Measured value: C (%): 62.84H (%): 2.31N (%): 9.58
MS(ESI):m/z 440.36[M+H]
+
IR(KBr,cm
-1):3059(C=C-H),1626,1553,1507,1421(C=C,C=N,C=O),1369.
2.R1-R16 preparation
Ir (acac) is added in the nitrogen still of anhydrous and oxygen-free
3, the one of the ligand L 1-L16 of 3 times amount amount of substances and 5 times amount anthracenes, be warming up to 300 DEG C of reaction 24h, methylene dichloride and sherwood oil (volume ratio 2:1), as eluent, are purified can be obtained title complex R1-R16 respectively by column chromatographies.
Compound warp
1h NMR, ultimate analysis, mass spectrum are verified, result shows that structure is correct, and data are as follows:
Title complex R1:
1H 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).
Results of elemental analyses: calculated value: C (%): 66.98H (%): 3.42N (%): 10.19
Measured value: C (%): 67.01H (%): 3.43N (%): 10.15
MS(MALDI-TOF):m/z1236.67(M
+)
Title complex R2:
1H 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).
Results of elemental analyses: calculated value: C (%): 69.21H (%): 4.73N (%): 8.97
Measured value: C (%): 69.18H (%): 4.75N (%): 8.99
MS(MALDI-TOF):m/z1404.68(M
+)
Title complex R3:
1H 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).
Results of elemental analyses: calculated value: C (%): 71.30H (%): 3.71N (%): 8.60
Measured value: C (%): 71.24H (%): 3.73N (%): 8.64
MS(MALDI-TOF):m/z1464.64(M
+)
Title complex R4:
1H 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).
Results of elemental analyses: calculated value: C (%): 65.89H (%): 3.00N (%): 12.81
Measured value: C (%): 65.83H (%): 3.05N (%): 12.84
MS(MALDI-TOF):m/z1311.27(M
+)
Title complex R5:
1H 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).
Results of elemental analyses: calculated value: C (%): 64.18H (%): 3.04N (%): 9.76
Measured value: C (%): 64.14H (%): 3.06N (%): 9.78
MS(MALDI-TOF):m/z1290.35(M
+)
Title complex R6:
1H 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).
Results of elemental analyses: calculated value: C (%): 60.00H (%): 2.73N (%): 8.75
Measured value: C (%): 59.94H (%): 2.75N (%): 8.78
MS(MALDI-TOF):m/z1440.36(M
+)
Title complex R7:
1H 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).
Results of elemental analyses: calculated value: C (%): 58.06H (%): 2.64N (%): 8.46
Measured value: C (%): 58.07H (%): 2.65N (%): 8.49
MS(MALDI-TOF):m/z1488.37(M
+)
Title complex R8:
1H 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).
Results of elemental analyses: calculated value: C (%): 61.60H (%): 2.70N (%): 9.37
Measured value: C (%): 61.56H (%): 2.72N (%): 9.38
MS(MALDI-TOF):m/z1344.27(M
+)
Title complex R9:
1H 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).
Results of elemental analyses: calculated value: C (%): 61.60H (%): 2.70N (%): 9.37
Measured value: C (%): 61.58H (%): 2.71N (%): 9.39
MS(MALDI-TOF):m/z1344.27(M
+)
Title complex R10:
1H 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).
Results of elemental analyses: calculated value: C (%): 54.75H (%): 2.21N (%): 7.66
Measured value: C (%): 54.73H (%): 2.22N (%): 7.68
MS(MALDI-TOF):m/z1644.35(M
+)
Title complex R11:
1H 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).
Results of elemental analyses: calculated value: C (%): 57.83H (%): 2.43N (%): 8.43
Measured value: C (%): 57.78H (%): 2.44N (%): 8.46
MS(MALDI-TOF):m/z1494.32(M
+)
Title complex R12:
1H 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).
Results of elemental analyses: calculated value: C (%): 59.23H (%): 2.38N (%): 9.01
Measured value: C (%): 59.20H (%): 2.40N (%): 9.03
MS(MALDI-TOF):m/z1398.31(M
+)
Title complex R13:
1H 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).
Results of elemental analyses: calculated value: C (%): 59.23H (%): 2.38N (%): 9.01
Measured value: C (%): 59.21H (%): 2.39N (%): 9.03
MS(MALDI-TOF):m/z1398.32(M
+)
Title complex R14:
1H 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).
Results of elemental analyses: calculated value: C (%): 57.03H (%): 2.08N (%): 8.67
Measured value: C (%): 57.00H (%): 2.09N (%): 8.68
MS(MALDI-TOF):m/z1453.22(M
+)
Title complex R15:
1H 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).
Results of elemental analyses: calculated value: C (%): 57.03H (%): 2.08N (%): 8.67
Measured value: C (%): 57.01H (%): 2.10N (%): 8.69
MS(MALDI-TOF):m/z1453.23(M
+)
Title complex R16:
1H 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).
Results of elemental analyses: calculated value: C (%): 54.99H (%): 1.81N (%): 8.36
Measured value: C (%): 54.95H (%): 1.83N (%): 8.38
MS(MALDI-TOF):m/z1507.18(M
+)
Embodiment two: the Fluorescent Characterization of title complex of the present invention
Testing tool is Hitachi F4600 luminoscope, the title complex of above-mentioned iridium to be dissolved in methylene dichloride (10
-5m) measure, at ambient temperature, emission peak positions is respectively:
Title complex R1:
λ
em, max, nm 633(is shown in accompanying drawing 2);
Title complex R2
λ
em, max, nm 633(is shown in accompanying drawing 2);
Title complex 3
λ
em, max, nm 647(is shown in accompanying drawing 2);
Title complex R16
λ
em, max, nm 613(is shown in accompanying drawing 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.
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| US20100270916A1 (en) * | 2009-04-28 | 2010-10-28 | Universal Display Corporation | Iridium complex with methyl-d3 substitution |
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| WO2006095943A1 (en) * | 2005-03-08 | 2006-09-14 | Lg Electronics Inc. | Red phosphorescene compounds and organic electroluminescence devices using the same |
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