The Importance of Electronic Dimensionality in Multiorbital Radical Conductors

Abstract

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Benzo[1,2,3]dithiazole Compounds: A History of Synthesis and Their Renewed Applicability in Materials and Synthetic Chemistry, Originating from the Herz Reaction

“…The R3c phase fared better at 10 −2 S cm −1 and, similarly to the Cmc21 sulphur analogue (Figure 13), became a metallic conductor at 6 GPa. A parallel investigation that included solids based on the benzobis[1,2,3]dithiazole neutral radicals (Scheme 29) was performed [111][112][113][114][115]. The desired 'brick wall' sheet structure (space group Cmc21, as in Figure 13) was formed with the fluoro substituent (30b, Table 5), which possessed marginally improved room-temperature conductivity (at A parallel investigation that included solids based on the benzobis [1,2,3]dithiazole neutral radicals (Scheme 29) was performed [111][112][113][114][115].…”

“…A parallel investigation that included solids based on the benzobis[1,2,3]dithiazole neutral radicals (Scheme 29) was performed [111][112][113][114][115]. The desired 'brick wall' sheet structure (space group Cmc21, as in Figure 13) was formed with the fluoro substituent (30b, Table 5), which possessed marginally improved room-temperature conductivity (at A parallel investigation that included solids based on the benzobis [1,2,3]dithiazole neutral radicals (Scheme 29) was performed [111][112][113][114][115]. The desired 'brick wall' sheet structure (space group Cmc2 1 , as in Figure 13) was formed with the fluoro substituent (30b, Table 5), which possessed marginally improved room-temperature conductivity (at 2 × 10 −2 S cm −1 ) compared to the Zwitterionic benzobisdithiazole solids (Scheme 29) [44,54,108].…”

“…The structures bearing bulkier substituents (30a (OAc), 30f (OMe) and 30g (SMe)) instead formed P2 1 /c crystals (as in Figure 14a) and thus acted as Mott insulators. Seven different benzobisdithiazoles were synthesised as the Herz salt, and each could be reduced to the neutral radical (30a-g, following an ion-exchange) electrochemically [111]; over time, a library of semi-conducting radical solids was built up across the publications (Table 5). [1,2,3]dithiazoyl radicals across several publications by Oakley et al [55,[111][112][113][114][115].…”

“…Percentages refer to pure isolated yields for the final reduction (radical formation) step. [1,2,3]dithiazoyl radicals across several publications by Oakley et al [55,[111][112][113][114][115].…”

“…a Synthesised using a quinone intermediate and then reduced with an electrochemical method [111]. b Reduced from the SbF 6 salt (rather than TfO) with a Fe-Cp complex rather than electrochemically [55].…”