A Tris-fused Donor System Composed of Two Tetrathiafulvalenes and an Extended Tetrathiafulvalene with an Anthraquinoid Spacer

Synthesis, Structures, and Electrochemical Properties of Bis‐ and Tetrakis(diphenylphosphino)tetrathiafulvalenes Extended with an Anthraquinoid Spacer

“…The simultaneous two‐electron transfer processes of 1 and 2 are irreversible, and the reversibility of these redox waves is enhanced when the voltammetry is carried out at a lower scan rate of 1 mV/s. These results are very similar to those reported for TTPAQ and TTPY‐1‐AQ, [5b,c] demonstrating that two different reduction processes depending on the scan rate can also be observed for TTFAQ derivatives without TTF moieties. From these results, we speculate that the reduction schemes of 1 and 2 are similar to those of TTPAQ and TTPY‐1‐AQ, as shown in Scheme 2 (for 1 as a representative).…”

“…The reduction process at a low scan rate is worthy of mention (Scheme 2). According to previous reports, [5b,c] the T‐form dication could be reduced to the S‐form neutral state by way of an S‐form cation radical. This was because a positive charge was located on the TTF moiety fused with the TTFAQ moiety to maintain a stable neutral S form of the latter.…”

“…We have developed various TTFAQ analogs and clarified their structures and electrochemical properties [5] . In particular, a bis‐ or tris‐fused donor system composed of one or two TTF(s) and one TTFAQ unit (TTPAQ and TTPY‐1‐AQ in Figure 2a) showed intriguing redox behavior [5b,c] . Taking the example of TTPAQ, two plausible reduction processes from the dication (T form) to the neutral state (S form) and neutral biradical (T form) were observed by cyclic voltammetry, whereas the corresponding oxidation was observed as a simultaneous two‐electron transfer process.…”

Synthesis and properties of tetrathiafulvalenes bearing 6-aryl-1,4-dithiafulvenes

“…Tetrathiafulvalenes (TTFs) with extended π-conjugation have attracted attention as possible components of functional materials, such as molecular conductors, field-effect transistors (FETs), and positive electrode materials for rechargeable batteries because the TTF moiety has strong electron-donating properties attributed to the formation of stable aromatic 1,3dithiol-2-ylidenes (1,3-dithiole rings) by one-and two-electron oxidation [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. Considerable efforts have been devoted to the development of peripherally benzene-or thiophene-substituted TTFs.…”

Synthesis and Properties of Tetrathiafulvalenes Bearing 6-Aryl-1,4-dithiafulvenes

“…Tetrathiafulvalene (TTF) with extended -conjugation have attracted attention as possible components for functional materials such as molecular conductors, field-effect transistor (FET), and positive electrode materials for rechargeable batteries, because the TTF moiety has strong electron-donating properties attributed to the formation of stable aromatic 1,3-dithiol-2-ylidenes (1,3-dithiole rings) by one-and two-electron oxidation [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. Considerable efforts have been devoted to the development of peripherally benzene-or thiophene-substituted TTFs.…”