How the Anchoring Site on Two Extended Tetrathiafulvalenes Impacts the Electronic Communication through a Bis(acetylide)ruthenium Linker

Abstract

Abstract:The interplay between two extended tetrathiafulvalenes connected, either from the dithiole rings or the

Redox-Switchable Bis-fused Tetrathiafulvalene Analogue: Observation and Control of Two Different Reduction Processes from Dication to Neutral State

“…Molecules that exhibit redox behavior accompanied by reversible structural change are promising components for switch units or memories in single molecular devices controlled by external electric fields . Nonplanar organic π-electron systems often exhibit unique electrochemical properties accompanied by a large conformational change. − A π-electron acceptor bianthrone is a representative example (Figure S1, Supporting Information). It adopts two conformations in the neutral state in different temperature regions.…”

“…As for π-electron donors, a tetrathiafulvalene (TTF) analogue with an anthraquinoid spacer ( 1 , Figure ; herein abbreviated as “TTFAQ”) exhibits a simultaneous two-electron oxidation accompanied by a conformational change . That is, (TTFAQ) 2+ has a conformation with an orthogonally twisted structure between the anthracene and the two 1,3-dithiolium rings (T-form), while the neutral TTFAQ adopts a folded saddle-like conformation (S-form). , The dication state of TTFAQ is thermodynamically more stable than the monocation state; in other words, the second redox potential ( E 2 ) is more negative than the first redox potential ( E 1 ) . This phenomenon is rarely observed in most π-electron donors, whose dications are less stable than monocations because of on-site Coulomb repulsion between two positive charges.…”

Rhenium-catalysed reactions in chemical synthesis: selected case studies

“…[38][39][40][41][42][43][44][45] Classical approaches for the synthesis of transition metal vinylidene complexes exploit 1,2-alkyl or 1,2-hydrogen shifts of internal, [46][47][48][49] or terminal alkynes. [50][51][52][53] These activation pathways are also often invoked in many associated transitionmetal-catalysed reactions employing alkyne substrates. [54][55][56][57] Jia and co-workers demonstrated the first example of C-C bond cleavage of internal propargyl alcohols to access rhenium viny-lidene complexes in 2018 (Scheme 1B).…”

A Dibenzotetrathiafulvalene-Bridged Bis(alkenylruthenium) Complex and Its One- and Two-Electron-Oxidized Forms

“…Best represented are ferrocenyl (Fc) derivatives with direct Fc-TTF connectivities or Fc-Arylene-TTF dyads. − In addition, the Lorcy group has published a series of elegant studies on ruthenium, platinum, and mercury complexes with one or two ethynyl-TTF or extended TTF (exTTF) ligands. Structures of the ruthenium complexes of relevance to the present work are summarized in Figure . − Mono- and bis-ethynyl (ex)­TTF ruthenium complexes possess a rich electrochemistry with one chemically reversible redox wave per Ru­(dppe) 2 and TTF constituent and significantly lower first oxidation potentials than any of their individual redox-active entities. Moreover, the unpaired spin densities and charge(s) of their one-electron-oxidized or one- and two-electron-oxidized forms are delocalized over all redox sites.…”