| 两个磷光铱配合物的合成和性质研究 |
| Synthesis and properties of two phosphorescence iridium complexes |
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| 摘要: 由于具有P=O键,二(二苯基膦酰)胺(tetraphenylimidodiphosphinate acid, Htpip)作为辅助配体引入Ir(III)配合物中,可以提高配合物的电子迁移率和器件的效率。本文采用氟取代的2-(4-氟苯基)吡啶(F4-ppy)为主配体、以Htpip和三氟甲基取代的Htfmtpip为辅助配体合成了两个铱配合物Ir(F4-ppy)2(tpip)和Ir(F4-ppy)2(tfmtpip)。晶体结构中Ir原子的配位几何构型均为八面体构型,Ir(F4-ppy)2(tpip)属于正交晶系 Pbca空间群,而Ir(F4-ppy)2(tfmtpip)属于单斜晶系P21/c空间群。配合物都具有较好的热稳定性,Ir(F4-ppy)2(tpip)和Ir(F4-ppy)2(tfmtpip)的初始分解温度分别为385 和395 oC。配合物Ir(F4-ppy)2(tfmtpip)的氧化和还原峰较配合物Ir(F4-ppy)2(tpip)分别向正电压移动了大约0.134和0.12 V,相应的HOMO和LUMO能级分别降低了0.14和0.43 eV。在室温、1×10-5 mol L-1的CH2Cl2溶液中Ir(F4-ppy)2(tpip)和Ir(F4-ppy)2(tfmtpip)的最大磷光发射峰分别位于492和495 nm,量子效率分别为9.2%和16.4%。结果表明在辅助配体上引入四个三氟甲基后不仅可以提高配合物的热稳定性和电化学稳定性,并且可以调控配合物的HOMO/LUMO能级和发光效率。 |
| 关键词: 二(二苯基磷酰)胺 2-(4-氟苯基)吡啶 铱配合物 晶体结构 电化学 磷光 |
| 基金项目: 国家自然科学基金;省自然科学基金 |
| Abstract: Due to the P=O bond, the introducing of tetraphenylimidodiphosphinate acid (Htpip) as the ancillary ligand can increase the electron mobility of the iridium complex and improve the organic light-emitting diode (OLED) performances. Using the 2-(4-fluorophenyl)pyridine (F4-ppy) as the cyclometalted ligand, Htpip and trifluoromethyl substituted Htfmtpip as the ancillary ligands, two Ir(III) complexes were synthesized and characterized. The complexes Ir(F4-ppy)2(tpip) and Ir(F4-ppy)2(tfmtpip) crystallize in the space groups Pbca of orthorhombic system and P21/c of monoclinic system, respectively, and the central Ir(III) atom occupies an octahedral coordination. Ir(F4-ppy)2(tpip) and Ir(F4-ppy)2(tfmtpip) show good thermal stability with decomposed temperatures of 385 and 395 oC, respectively. Compared with Ir(F4-ppy)2(tpip), the oxidation and reduction peaks of Ir(F4-ppy)2(tfmtpip) shift to the positive range and the HOMO/LUMO energy levels are decreased from -5.55/-2.92 eV to -5.41/-2.49 eV. In the CH2Cl2 solution (1×10-5 mol L-1) the maximum phosphorescence peaks of Ir(F4-ppy)2(tpip) and Ir(F4-ppy)2(tfmtpip) locat at 492 and 495 nm with quantum efficiencies of 9.2% and 16.4% at room temperature, respectively. The results prove that the introducing of –CF3 moieties to the ancillary ligand can increase the thermal/electrochemical stability, manipulate the HOMO/LUMO energy levels and improve the luminescence efficiency of the Ir(III) complex. |
| Keywords: tetraphenylimidodiphosphinate acid 2-(4-fluorophenyl)pyridine iridium complex crystal structure electrochemistry phosphorescence |
| 投稿时间：2014-03-27 修订日期：2014-05-08 |
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