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设计并制备三种具不同官能团的铱[III]邻菲啰啉配合物:[Ir(ppy)2phen-Br]Cl,[Ir(ppy)2phen-COOH]Cl,[Ir(ppy)2phen-Si]Cl,以及对比参照物[Ir(ppy)2phen-NH2]Cl.其中,ppy为2-苯基吡啶,phen-Br为2-溴-2甲基-N-(1,10-菲啰啉-5-基)丙酰胺,phen-COOH为4-[(1,10-菲啰啉-5-基)氨基]-4-酰基丁烯酸,phen-Si为5-[N,N-二-3-(三乙氧硅)基]酰亚胺-1,10-菲啰啉,phen-NH2为5-氨基-邻菲啰啉,并采用核磁共振(NMR)、质谱(MS)、紫外-可见(UV-Vis)吸收光谱、荧光(PL)光谱法和循环伏安法(CV)等对上述配合物进行了分析和表征.光物理性能研究结果表明:这些配合物在蓝-紫色可见光区域有较强吸收,可发射出明亮的黄色到橙红色荧光,量子效率达到12%以上.相比较于参照物[Ir(ppy)2phen-NH2]Cl(5.78μs),三种新型配合物在量子效率未明显降低甚至提高的前提下,荧光寿命有了显著的提高(9.18–12.00μs).其中,[Ir(ppy)2phen-Br]Cl(1)不但有最高的荧光量子产率(32%)和最长的荧光寿命(12.00μs),而且也具有最好的氧传感性能,I0/I(无氧与纯氧条件下的荧光强度比值)可达到10.91.这使得[Ir(ppy)2phen-Br]Cl有望成为接枝型,较高性能的光学氧传感器的候选氧敏指示剂.除此之外,还通过含时密度泛函理论(TD-DFT)计算对配合物光电性能进行补充说明,理论计算表明:这些配合物是以铱为中心的近似八面体结构,理论计算结果与实际实验数据相一致.
[Ir (ppy) 2phen-Br] Cl, [Ir (ppy) 2phen-COOH] Cl and [Ir (ppy) 2phen-Si ] Cl and a comparative reference [Ir (ppy) 2phen-NH2] Cl wherein ppy is 2-phenylpyridine and phen-Br is 2-bromo-2methyl-N- (1,10-phenanthroline Phen-COOH is 4 - [(1,10-phenanthrolin-5-yl) amino] -4-acyl crotonic acid and phen-Si is 5- [N, (Triethoxysilyl) imide-1,10-phenanthroline, and phen-NH2 is 5-amino-phenanthroline. The structures of these compounds were characterized by means of nuclear magnetic resonance (NMR), mass spectrometry The complexes were analyzed and characterized by UV-Vis absorption spectroscopy, fluorescence (PL) spectroscopy and cyclic voltammetry (CV). The results of photophysical properties show that these complexes are effective in blue-violet visible light The region has strong absorption, can emit bright yellow to orange-red fluorescence, the quantum efficiency of more than 12% .Compared with the reference [Ir (ppy) 2phen-NH2] Cl (5.78μs), three new complexes in (9.18-12.00μs). Under these conditions, [Ir (ppy) 2phen-Br] Cl (1) not only has the highest fluorescence quantum yield ( 32%) and the longest fluorescence lifetime (12.00 μs), but also has the best oxygen sensing performance, with a ratio of I0 / I (fluorescence intensity ratio under anaerobic and pure oxygen conditions) of 10.91. ppy) 2phen-Br] Cl is expected to be a candidate oxygen sensitive indicator for the grafted, higher performance optical oxygen sensor.In addition to this, the photoconductivity of the complex is calculated by time-dependent density functional theory (TD-DFT) The theoretical calculation shows that these complexes are approximate octahedral structures centered on iridium. The theoretical calculation results are consistent with the actual experimental data.