The first methyl antimony linked dimeric tetrathiafulvalene and tetraselenafulvalenes

Tetrathiafulvalene Dimer Merged with a Binuclear Ring of Sn and Sb: Synthesis and Molecular Structures Induced by Heteroatoms

“…Since isomerization between the cis and trans isomers was not observed upon heating of a solution of cis ‐ 2a [D 4 ]tetrachloroethane to 140 °C in a VT‐NMR experiment, the isomerization barrier could be high. This tendency was consistent with the other diantimony ring found in the literature , . Similarly, upon cooling of a solution of cis ‐ 2a in CD 2 Cl 2 to –90 °C, signals corresponding to the tolyl and TTF groups did not change except for a slight signal broadening in the 1 H NMR spectra.…”

“…Therefore, to obtain a dimeric TTF system with high dimensionality in the solid state, we envisaged the replacement of Sn with a trivalent Sb III as a promising strategy for the enhancement of intermolecular interactions because of its large van der Waals distance and the available sites on an Sb atom. Previously, Ashizawa and Kato reported the first synthesis of a doubly methyl‐antimony (MeSb)‐bridged TSF dimer ( 3 ) and singly methyl‐antimony‐bridged TTF . Compound 3 was prepared in a one‐pot reaction of bislithiated TSF with MeSbI 2 .…”

Tetrathiafulvalene-based group XV ligands: Synthesis, coordination chemistry and radical cation salts

“…Dimeric TTF and tetraselenafulvalenes (TSFs) linked by a single or a double methylantimony bridge have been described recently by Ashikawa et al [94]. Compound 113 was obtained from the reaction of the lithium derivative of TTF with 0.5 equivalent of MeSbI 2 .…”

Intramolecular Mixed‐Valence State Through Silicon or Germanium Double Bridges in Rigid Bis(Tetrathiafulvalenes)

“…Alternatively, two tetraselenafulvalene (TSF) units have been connected through methylantimony groups to provide (MeSb) 2 A C H T U N G T R E N N U N G (TSF) 2 . [11] Nevertheless, within all the heteroatom containing rigid dimeric bisA C H T U N G T R E N N U N G (TTF) described so far, no clear evidence, such as EPR measurements, for the electron delocalization throughout both TTF units in the radical-cation species has been provided. Highly appealing heteroatombased bridges consist of dialkylsilicon or dialkylgermanium linkers.…”

“…[12] Moreover, the use of R 2 Si or R 2 Ge bridges would avoid the formation of cis/trans isomers encountered in the case of (PPh) 2 A C H T U N G T R E N N U N G (o-DMTTF) 2 [10] or (MeSb) 2 -A C H T U N G T R E N N U N G (TSF) 2 . [11] We report herein the synthesis of unprecedented rigid dimeric TTFs formulated as (Me 2 Si) 2 A C H T U N G T R E N N U N G (o-DMTTF) 2 and (Me 2 Ge) 2 A C H T U N G T R E N N U N G (o-DMTTF) 2 . The latter also represents the first germanium-containing TTF derivative.…”