10.1021/ic5013044.s001
Yifei Liu
Yifei
Liu
Cheikh
Mbacké Ndiaye
Cheikh
Mbacké
Ndiaye
Corinne Lagrost
Corinne
Lagrost
Karine Costuas
Karine
Costuas
Sylvie Choua
Sylvie
Choua
Philippe Turek
Philippe
Turek
Lucie Norel
Lucie
Norel
Stéphane Rigaut
Stéphane
Rigaut
Diarylethene-Containing
Carbon-Rich Ruthenium Organometallics:
Tuning of Electrochromism
American Chemical Society
2014
EPR
UV
DTE
ligand
oxidation
quantum chemical calculations
electrochemical cyclization
electrochemical ring closure
EEC
2014-08-04 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Diarylethene_Containing_Carbon_Rich_Ruthenium_Organometallics_Tuning_of_Electrochromism/2268772
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]-CC-DTE-CC-[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–vis–NIR–IR
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 <i>trans</i> 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.