具不同官能团钌(Ⅱ)邻菲啰啉配合物氧淬灭性能的比较研究

Comparison Study of Oxygen Quenching of Ru(Ⅱ) Phenanthroline Complexes with Different Functional Groups

设计并制备具不同官能团的钌(Ⅱ)邻菲啰啉配合物——[Ru(bpy)2(phen-NO2)](PF6)2(1),[Ru(bpy)2(phen-Br)](PF6)2(2),[Ru(bpy)2(phen-NH2)](PF6)2(3),[Ru(bpy)2(bphen)](PF6)2(4),其中,bpy为2,2'-联吡啶,phen-NO2为5-硝基-邻菲啰啉,phen-Br为5-溴-1,10-菲啰啉,phen-NH2为5-氨基-邻菲啰啉,bphen为4,7-二苯基-邻菲啰啉.借助核磁共振(NMR)、红外光谱(FTIR)、元素分析、紫外可见光谱(UV-vis)和荧光光谱法对其进行了分析与表征.结果表明:配合物2～4在蓝-紫色可见光区域有较强吸收、可发射出明亮的橙红色荧光、具荧光量子效率(Φ)高、激发态寿命(τ)长、Stocks位移值较大(147～180 nm)和优良的氧致荧光淬灭性能(Ksv≥3.5,(I0/I)max≥4.0)等光物理性质.其中,具接枝型官能团氨基的配合物3的量子效率(Φ)=10%,τ=381.8 ns,Ksv=3.49,(I0/I)max=4.33;而溴修饰的配合物2以高达18%的荧光量子效率、634.7 ns的激发态寿命、180 nm的Stocks位移和Ksv=4.59,氧淬灭参数(I0/I)max=5.29,使之最有希望成为接枝型、较高性能的光学氧传感器的候选氧敏指示剂.

Ruthenium（Ⅱ） phenanthroline complexes with different functional groups： [Ru（bpy）2（phen- NO2）]（PF6）2 （1）, [Ru（bpy）2（phen-Br）]（PF6）2 （2）, [Ru（bpy）2（phen-NH2）]（PF6）2 （3）, [Ru（bpy）2（bphen）]（PF6）2 （4） （where bpy= 2,2＇-bipyridyl, phen-NO2= 5-nitro-phenanthroline, phen-Br= 5-bromo-phenanthroline, phen_NH2=5_amino_phenanthroline, bphen=bathophenanthroline） were synthesized. They were characterized and analyzed by NMR, FTIR, elemental analysis and UV-Vis absorption and photoluminesence spectroscopy measurements, respectively. The investigations indicate that complexes 2-4 emit bright or- ange-red fluorescence and have intensely visible absorption in blue-purple region. Complexes 2-4 show the photophysics properties of high quantum efficiencies （φ）, long excited-state luminescence lifetime （r）, large Stocks shift （147-205 nm） and good oxygen-induced luminescence quenching properties （Ksv 〉/3.5, （I0/I）max≥4.0）. Among them, complex 3 grafted by an amino functional group has a Ф of 10%, a τ of 381.8 ns, a Ksv of 3.49 and the maximum I0/I factor of 4.33. However, complex 2 grafted by a bromine group shows higher Ф of 18%, longer luminescence r of 635 ns, larger Ksv of 4.59 and the maximum I0/I factor up to 5.29. These properties make it a promising fluorescence indicator applied in grafting and high perform-ance optics oxygen sensor.