Goze Christine, Dupont Nathalie, Beitler Elvira, Leiggener Claudia, Jia Hongpeng, Monbaron Philippe, Liu Shi-Xia, Neels Antonia, Hauser Andreas, Decurtins Silvio
Departement fur Chemie und Biochemie, Universitat Bern, Freiestrasse 3, CH-3012 Bern, Switzerland.
Inorg Chem. 2008 Dec 1;47(23):11010-7. doi: 10.1021/ic801252t.
A pi-extended, redox-active bridging ligand 4',5'-bis(propylthio)tetrathiafulvenyl[i]dipyrido[2,3-a:3',2'-c]phenazine (L) was prepared via direct Schiff-base condensation of the corresponding diamine-tetrathiafulvalene (TTF) precursor with 4,7-phenanthroline-5,6-dione. Reactions of L with [Ru(bpy)(2)Cl(2)] afforded its stable mono- and dinuclear ruthenium(II) complexes 1 and 2. They have been fully characterized, and their photophysical and electrochemical properties are reported together with those of Ru(bpy)(2)(ppb) and Ru(bpy)(2)(mu-ppb)Ru(bpy)(2) (ppb = dipyrido[2,3-a:3',2'-c]phenazine) for comparison. In all cases, the first excited state corresponds to an intramolecular TTF --> ppb charge-transfer state. Both ruthenium(II) complexes show two strong and well-separated metal-to-ligand charge-transfer (MLCT) absorption bands, whereas the (3)MLCT luminescence is strongly quenched via electron transfer from the TTF subunit. Clearly, the transient absorption spectra illustrate the role of the TTF fragment as an electron donor, which induces a triplet intraligand charge-transfer state ((3)ILCT) with lifetimes of approximately 200 and 50 ns for mono- and dinuclear ruthenium(II) complexes, respectively.
通过相应的二胺 - 四硫富瓦烯（TTF）前体与4,7 - 菲咯啉 - 5,6 - 二酮直接进行席夫碱缩合反应，制备了一种π - 扩展的、具有氧化还原活性的桥连配体4',5'-双（丙硫基）四硫富瓦烯并[ i ]二吡啶并[2,3 - a:3',2'- c]吩嗪（L）。L与[Ru(bpy)₂Cl₂]反应得到其稳定的单核和双核钌（II）配合物1和2。它们已得到充分表征，并报告了其光物理和电化学性质，同时还给出了[Ru(bpy)₂(ppb)]²⁺和[Ru(bpy)₂(μ - ppb)Ru(bpy)₂]⁴⁺（ppb = 二吡啶并[2,3 - a:3',2'- c]吩嗪）的相关性质用于比较。在所有情况下，第一激发态对应于分子内TTF→ppb电荷转移态。两种钌（II）配合物均显示出两个强且分离良好的金属到配体电荷转移（MLCT）吸收带，而³MLCT发光通过从TTF亚基的电子转移而强烈猝灭。显然，瞬态吸收光谱说明了TTF片段作为电子供体的作用，对于单核和双核钌（II）配合物，它分别诱导了寿命约为200和50 ns的三重态配体内电荷转移态（³ILCT）。
