The Roles of Molecular Structure and Effective Optical Symmetry in Evolving Dipolar Chromophoric Building Blocks to Potent Octopolar Nonlinear Optical Chromophores
作者:Tomoya Ishizuka、Louise E. Sinks、Kai Song、Sheng-Ting Hung、Animesh Nayak、Koen Clays、Michael J. Therien
DOI:10.1021/ja105004k
日期:2011.3.9
A series of mono-, bis-, tris-, and tetrakis(porphinato)zinc(II) (PZn)-elaborated ruthenium(II) bis(terpyridine) (Ru) complexes have been synthesized in which an ethyne unit connects the macrocycle meso carbon atom to terpyridyl (tpy) 4-, 4'-, and 4''-positions. These supermolecular chromophores, based on the ruthenium(II) [5-(4'-ethynyl-(2,2';6',2''-terpyridinyl))-10,20-bis(2',6'-bis(3,3-dimethyl
已经合成了一系列单、双、三和四(卟啉)锌(II)(PZn)-精心制作的钌(II)双(三联吡啶)(Ru)配合物,其中乙炔单元连接大环内消旋碳原子到三联吡啶 (tpy) 4-、4'-和 4''-位。这些基于钌 (II) [5-(4'-乙炔基-(2,2';6',2''-三联吡啶))-10,20-bis(2',6'-bis (3,3-二甲基-1-丁氧基)苯基)卟吩基]锌(II)-(2,2';6',2''-三联吡啶)(2+)双六氟磷酸盐(RuPZn)原型,表现出强烈混合PZn 基振荡器强度与钌三联吡啶电荷共振带的关系。电位和线性吸收光谱数据表明,对于多个 PZn 部分通过乙炔连接到 [Ru(tpy)(2)](2+) 核的结构,PZn 单元之间几乎没有电子耦合,无论它们位于相同还是相反的 tpy 配体上。与这些实验一致,泵浦探针瞬态吸收研究表明,这些结构的单个 RuPZn 片段充其量只表现出适度的激发