Toward molecular wire: Synthesis, crystal, molecular, and π-electronic structure of 1,7-bis(aryl)-1,3,5,7-tetraaza-2,4,6-trithia-1,2,5,6-heptatetraenes

✍ Scribed by Andrey V. Zibarev; Alexey O. Miller; Yuri V. Gatilov; Georgii G. Furin

• Publisher: John Wiley and Sons
• Year: 1990
• Tongue: English
• Weight: 855 KB
• Volume: 1
• Category: Article
• ISSN: 1042-7163
• DOI: 10.1002/hc.520010604

✦ Synopsis

The title compounds were obtained by the reaction of I -aryl-3-trimethylsilyl-l,3-diaza-2-thiaallenes with dichloromonosulfane or 1 -aryl-4-(1 -phtalimidyl)-l,3diaza-2,4-dithia-l,2-butadienes in the presence ofCsF. The latter route also afforded nonsyinmetric derivatives. In contrast, the reaction of N,N,N',N'-tetrakis(trimethylsi1yl)diaininosulfane with S,S-dichloro-N-auyliminosulfuranes ( I :2) led to 1 J-bis(aryl)-I ,3-diaza-2-thiaallenes and cyclotetra(azathiene). As shown bv the X-ray structure analysis, the molecule of the title compound with Ar = Ph is planar, with configuration of the azathiene chain being similar to that of'polv(azathiene) (SN),. The MNDO calculations indicate that most of the IT-MOs ofthis compound, including the frontier ones, are delocalized throughout the whole molecule. The data obtained confirm the possibilitv o f creating molecular wire for molecular electronic devices on the basis of extended acvclic azathienes. A n attempt to synthesize more extended compounds than the title ones resulted in spontaneous shortening of their azathiene chains.