Oligophenyls with Multiple Disulfide Bridges as Higher Homologues of Dibenzo[c,e][1,2]dithiin: Synthesis and Application in Lithium‐Ion Batteries

Abstract

Higher homologues of dibenzo[ c , e ][1,2]dithiin were synthesized from oligophenyls bearing multiple methylthio groups. Single‐crystal X‐ray analyses revealed their nonplanar structures and helical enantiomers of higher meta ‐congener 6 . Such dibenzo[1,2]dithiin homologues are demonstrated to be applicable to lithium‐ion batteries as cathode, displaying a high capacity of 118 mAh g −1 at a current density of 50 mA g −1 .

Self-Resetting Bistable Redox Molecular Machines for Fullerene Recognition

“…The model we propose herein, again driven by nature’s inspirational influence, is based on the formation and cleavage of disulfide (S–S) bridges . It is well-known that this motif is present in a vast assortment of biomolecules, especially in proteins, whose function is to provide stability to the molecule favoring the maturation (correct folding) progress toward their native state. , The variety of protocols to include the S–S motif, either chemically or electrochemically, in synthetic compounds is widespread , and has been successfully applied in a variety of outstanding concepts. , Corannulene chalcogenides, especially those bearing sulfur as the distinctive heteroatom, have been extensively studied due to their special electronic features when compared to the parent buckybowl, leading to materials with distinctive properties. − One of the most interesting characteristics is their electron donation ability to form stable adducts with fullerenes. − …”

Accumulation of Four Electrons on a Terphenyl (Bis)disulfide

“…The bis(disulfide) terph(S 2 ) 2 (Scheme 1 ) was previously prepared following a different synthetic procedure than we employed in our work presented here. [70] The previous report did not include electrochemical studies geared at elucidating potential inversion and multi‐electron storage on the terph(S 2 ) 2 compound, and no photochemical investigations were made.…”

“…The analytical data are in good agreement with the previously reported characterization of terph(S 2 ) 2 . [70] The earlier employed procedure was based on methyl‐protected thiols that can be used for Pd‐catalyzed C−C cross coupling reactions, which can be challenging with the typical Newman‐Kwart compounds, because some of them seem to interfere with the Pd‐based catalytic cycle. [72] …”

“…[20,28,[66][67][68][69] Herein, we present electro-and photochemical investigations of a p-terphenyl-based (bis)disulfide compound that represents an extension of the known molecular acceptor units from one to two disulfides (terph(S 2 ) 2 , Figure 1b), in order to accumulate up to four electrons. [70] We describe the synthesis of terph(S 2 ) 2 , which is then structurally characterized and thoroughly investigated in terms of its redox chemistry. Controlled potential coulometry paired with digital simulations of the cyclic voltammograms reveal two consecutive two-electron reduction processes, occurring with potential inversion and potential compression.…”

“…Herein, we present electro‐ and photochemical investigations of a p ‐terphenyl‐based (bis)disulfide compound that represents an extension of the known molecular acceptor units from one to two disulfides (terph(S 2 ) 2 , Figure 1b), in order to accumulate up to four electrons [70] . We describe the synthesis of terph(S 2 ) 2 , which is then structurally characterized and thoroughly investigated in terms of its redox chemistry.…”