Influence of the “Innocent” Ligands on the MLCT Excited-State Behavior of Mono(bipyridine)ruthenium(II) Complexes: A Comparison of X-ray Structures and 77 K Luminescence Properties
作者:Yuan-Jang Chen、Puhui Xie、Mary Jane Heeg、John F. Endicott
DOI:10.1021/ic0602547
日期:2006.8.1
2-bipyridine (bpy) ligands (for distortion modes near 1500 cm(-1)) in the metal-to-ligand charge-transfer (MLCT) excited states for a series of complexes with the same ruthenium(II) bipyridine chromophore. The bpy ligand is nearly planar in the X-ray structures of the complexes with (L)4 = (NH3)4, triethylenetetraamine (trien), and 1,4,7,10-tetraazacyclododecane ([12]aneN4). However, for (L)4 = 5,12-rac-5,7,7
已显示[Ru(L)4bpy] 2+配合物的非发色配体的变化会导致发射带形状发生较大变化,即使发射能量相似也是如此。通过从观察到的发射光谱中生成经验重组能量分布图(emrep),系统地检查了这些能带形状的变化(Xie,P .;等人,J。Phys。Chem。A 2005,109,4671),其中这些配置文件提供了方便的探针,用于从金属到配体的电荷转移(2,2-联吡啶(bpy)配体的基态结构的畸变差异(对于1500 cm(-1)附近的畸变模式)) MLCT)具有相同钌(II)联吡啶发色团的一系列配合物的激发态。bpy配体在(L)4 =(NH3)4,三亚乙基四胺(trien),和1,4,7,10-四氮杂环十二烷([12] aneN4)。然而,对于(L)4 = 5,12-rac-5,7,7,12,14,14-六甲基-1,4,8,11-四氮杂环十四烷,X射线晶体结构显示bpy配体为在基态中扭曲(甲基/