Electronically Coupled Tetrathiafulvalene Electrophores across a Non-innocent Acetylide–Ruthenium Bridge

摘要: The synthesis and structural characterization of trans-[Ru(C≡CMe3TTF)2(dppe)2] (HC≡CMe3TTF = 4-ethynyl-4′,5,5′-trimethyltetrathiafulvalene) are described together with the X-ray crystal structures organic pro-ligands. Cyclic voltammetry experiments show sequential oxidation neutral compound five one-electron processes up to corresponding pentacation, trans-[Ru(III)(C≡CMe3TTF)2(dppe)2]5+, evidencing electronic interactions among three coupled electrophores, two TTFs Ru(II) center. A strong effect supporting electrolyte in dichloromethane was observed on ΔE values especially between second third steps fourth one, when [NBu4][PF6] substituted for Na[B(C6H4(CF3)2)4]. This indicates appreciable role ion-pairing play stabilizing these higher charge states, although solvation factors have been shown be less significant this case. separation first redox events essentially independent medium effects, indicating a more significant, inherent intramolecular effect. combined spectroscopic computational investigations evidenced that (i) metal-based electroactive sites strongly electronically (ii) bisacetylide-ruthenium linker efficiently mediates coupling tetrathiafulvalenes.