Structure and photophysics of near-infrared emissive ytterbium(iii) monoporphyrinate acetate complexes having neutral bidentate ligands
作者:Hongshan He、Andrew G. Sykes、P. Stanley May、Guishan He
DOI:10.1039/b909243a
日期:——
Substitution reactions between [Yb(TPP)(OOCCH3)(CH3OH)2] (1) and neutral bidentate ligands NN led to the formation of monoporphyrinate ytterbium(III) complexes [Yb(TPP)(OOCCH3)(NN)] (TPP = 5,10,15,20-tetraphenylporphyrinate anion; NN = 4-methyl-1,10-phenanthroline (2), 1,10-phenanthroline (3), 4,7-dimethyl-1,10-phenanthroline (4), 5,6-epoxy-5,6-dihydroxy-1,10-phenanthroline (5) and 2,2′-dipyridylamine (6)). Single-crystal X-ray diffraction analysis revealed that ytterbium(III) ions in 1 and 6 were seven-coordinate with OOCCH3− in monodentate coordination, whereas those in 2, 3, 4 and 5 were eight-coordinate with OOCCH3− in bidentate coordination. The visible emission (650 and 720 nm) from the porphyrin and near-infrared (NIR) emission (980 and 1003 nm) from ytterbium(III) ion were observed for all complexes. The eight-coordinate complexes exhibited stronger NIR emission and longer lifetimes in toluene solution than the seven-coordinate complexes. The NIR emission of complexes with decreased lifetimes was also observed when they were blended into organic polymer PMMA.
[Yb(TPP)(OOCCH3)(CH3OH)2](1)与中性双齿配体 NN 之间的取代反应导致形成单卟啉酸镱(III)配合物 [Yb(TPP)(OOCCH3)(NN)](TPP = 5,10,15,20-四苯基卟啉酸阴离子;NN = 4-甲基-1,10-菲罗啉 (2)、1,10-菲罗啉 (3)、4,7-二甲基-1,10-菲罗啉 (4)、5,6-环氧-5,6-二羟基-1,10-菲罗啉 (5) 和 2,2′-二吡啶基胺 (6))。单晶 X 射线衍射分析表明,1 和 6 中的镱(III)离子与 OOCCH3- 呈单配位,为七配位;而 2、3、4 和 5 中的镱(III)离子与 OOCCH3- 呈双配位,为八配位。所有配合物都能观察到卟啉的可见光发射(650 纳米和 720 纳米)和镱(III)离子的近红外发射(980 纳米和 1003 纳米)。与七配位配合物相比,八配位配合物在甲苯溶液中的近红外发射更强,寿命更长。将这些配合物与有机聚合物 PMMA 混合后,还观察到配合物的近红外发射和寿命缩短。