Diruthenium Complexes with π-Extended Bridging Bis(alkenyl)arylene Ligands, A Derived Metallamacrocycle, and Their Oxidized Forms

• DOI: 10.1021/acs.organomet.3c00337
• Publication Date: 2023-10-27T18:41:43Z
• Authors: Franciska S. Gogesch; Sebastian Schwab; Anja Rehse; Michael Linseis; Ananya Baksi; Guido H. Clever; Rainer F. Winter
• Keywords: Arylene

We report on dinuclear alkenylruthenium complexes with π-extended trans,trans-distyrylbenzene (1-V) or 1,4-(2-phenylethynyl)benzene (1-A) linkers akin to oligophenylvinylene and oligophenylethynylene oligomers (OPV-3 OPE-3, respectively) the macrocylic analogue 2-A. All compounds were characterized by NMR spectroscopy high-resolution ESI-MS. Their electrochemical spectroscopic properties examined. The efficacy of intramolecular through-bond electron transfer in their mixed-valent, one-electron-oxidized radical cations was probed UV/vis/NIR EPR as well density functional theory calculations. terminally appended diruthenium tags present add IR available toolbox provide resolved hyperfine splittings 31P nuclei spectra one- two-electron-oxidized dications. Our results indicate charge localization one {Ru}–CH═CHAr site time scale for [1-A]•+ [2-A]••2+ a small degree delocalization [1-V]•+. On slower spectroscopy, [1-V]•+ become valence-detrapped nearly so. near breakdown electronic coupling fast scales is also indicated finding that chromophores [1-V]2+, [1-A]2+, [2-A]4+ are mutually identical.