Synthesis, structure and properties of a novel trisulfide double-bridged TTF dimer

Abstract

We have synthesized novel trisulfide-bridged tetrathiafulvalene (TTF) dimer molecule in which two TTF moieties are connected to each other by two trisulfide chains. X-Ray crystal structure analysis reveals that the molecule has a unique cyclophane-like U-shape structure. The structure of the ClO 4 salt is also described.Research towards new donors for organic conductors based on the tetrathiafulvalene (TTF) framework has been actively pursued since the discovery of the metallic TTF-tetracyanoquinodimethane complex.1 Among them, the synthesis of tetrathiafulvalenophane was first reported in 1980 and extensively developed in the 1990s because of its unusual molecular structure and interesting intramolecular interaction.2,3 In particular several of these compounds have molecular structures like the dimeric structure of the coventional conducting salts such as the k-type bis(ethylenedithio)-TTF salts,4 which is related to the strong electron correlation system and Mott

Synthesis, Structure, Optical, and Electrochemical Properties of Triple‐ and Quadruple‐Decker Co‐facial Tetrathiafulvalene Arrays

“…Two TTFs are oriented parallel to each other with a suitable separation of approximately 3.5 Å. This face‐to‐face dimeric geometry is quite similar to the molecular structure of the π‐dimer composed of trisulfide double‐bridged TTF 16 2+ crystallized with ClO 4 − reported by Fujiwara and Kobayashi . In addition, the calculated face‐to‐face dimeric geometry of 2Ma 2+ is somewhat stabilized by a close S⋅⋅⋅H contact at the linker moiety (Figure b).…”

“…This face-to-facedimeric geometry is quite similar to the molecular structure of the p-dimerc omposed of trisulfide double-bridged TTF 16 2 + crystallized with ClO 4 À reported by Fujiwaraa nd Kobayashi. [21] In addition, the calculated faceto-face dimeric geometry of 2Ma 2 + is somewhat stabilized by ac lose S···H contact at the linker moiety ( Figure 10 b). Hence, such geometricalp reference may produce at riple-or quadruple-decker mode in which charge/electrons can delocalize through the mutual interactions in the presentt rimeric and tetrameric systems.…”

Molecular Electrochemistry of Cyclophanes

“…On the other hand, if the linker structure distorts one TTF unit, as the right hand one in 17 (X = -(CH 2 ) 2 -), the CV signals split and up to four peaks are observed [49]. Peak splitting is also apparent if the two TTF units do electronically interact (18) [50,51]. The interaction is usually stronger in the oxidized form than in the neutral starting compound [52], in accordance with Hückel MO calculations [53].…”

Fluorine Segregation in Crystalline Materials: Structural Control and Solid‐State [2+2] Cycloaddition in CF3‐Substituted Tetrathiafulvalene Derivatives

“…This DE value largely exceeds those reported for comparable TTF dimers and cyclophanes such as compounds 14-17 (Scheme 8 and Table 3) where the two TTF redox centers are constrained in a face-to-face conformation. [56][57][58][59] The main difference between compounds 14-17 and compound (EE)-13 is in the very close proximity of the redox moieties in compound (EE)-13 due to the cyclobutane ring and also in its increased rigidity while molecules 14-17 still exhibit degrees of freedom.…”