Institute of Organic Chemistry II and Advanced Materials, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany.
Beilstein J Org Chem. 2013 May 6;9:866-76. doi: 10.3762/bjoc.9.100. Print 2013.
Pd-catalyzed Sonogashira cross-coupling reactions were used to synthesize novel π-conjugated oligothienylene-ethynylene dendrons and their corresponding terpyridine-based ligands. Their complexation with Ru(II) led to interesting novel metallodendrimers with rich spectroscopic properties. All new compounds were fully characterized by (1)H and (13)C NMR, as well as MALDI-TOF mass spectra. Density functional theory (DFT) calculations performed on these complexes gave more insight into the molecular orbital distributions. Photophysical and electrochemical studies were carried out in order to elucidate structure-property relationships and the effect of the dendritic structure on the metal complexes. Photophysical studies of the complexes revealed broad absorption spectra covering from 250 to 600 nm and high molar extinction coefficients. The MLCT emission of these complexes were significantly red-shifted (up to 115 nm) compared to the parent Ru(tpy)2 complex.
钯催化的 Sonogashira 交叉偶联反应被用于合成新型的π共轭寡噻吩-乙炔基树枝状分子及其相应的三联吡啶基配体。它们与 Ru(II) 的络合导致了具有丰富光谱性质的新型金属树枝状大分子。所有新化合物都通过 1H 和 13C NMR 以及 MALDI-TOF 质谱进行了充分表征。对这些配合物进行的密度泛函理论（DFT）计算提供了更多关于分子轨道分布的见解。为了阐明结构-性质关系以及树枝状结构对金属配合物的影响，进行了光物理和电化学研究。配合物的光物理研究表明，其吸收光谱从 250nm 到 600nm 很宽，摩尔消光系数很高。与母体 Ru(tpy)2 配合物相比，这些配合物的 MLCT 发射明显红移（高达 115nm）。
