Diarylethene-Containing Carbon-Rich Ruthenium Organometallics: Tuning of Electrochromism

详细信息    查看全文

• 作者：Yifei Liu ; Cheikh Mback茅 Ndiaye ; Corinne Lagrost ; Karine Costuas ; Sylvie Choua ; Philippe Turek ; Lucie Norel ; St茅phane Rigaut
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：August 4, 2014
• 年：2014
• 卷：53
• 期：15
• 页码：8172-8188
• 全文大小：832K
• ISSN：1520-510X

文摘

The association of a dithienylethene (DTE) system with ruthenium carbon-rich systems allows reaching sophisticated and efficient light- and electro-triggered multifunctional switches R-[Ru]-C鈮-DTE-C鈮-[Ru]-R, featuring multicolor electrochromism and electrochemical cyclization at remarkably low voltage. The spin density on the DTE ligand and the energetic stabilization of the system upon oxidation could be manipulated to influence the closing event, owing to the noninnocent behavior of carbon-rich ligands in the redox processes. A combination of spectroscopic (UV鈥搗is鈥揘IR鈥揑R and EPR) and electrochemical studies, with the help of quantum chemical calculations, demonstrates that one can control and get a deeper understanding of the electrochemical ring closure with a slight modification of ligands remote from the DTE unit. This electrochemical cyclization was established to occur in the second oxidized state (EEC mechanism), and the kinetic rate constant in solution was measured. Importantly, these complexes provide an unprecedented experimental means to directly probe the remarkable efficiency of electronic (spin) delocalization between two trans carbon-rich ligands through a metal atom, in full agreement with the theoretical predictions. In addition, when no cyclization occurs upon oxidation, we could achieve a redox-triggered magnetic switch.