Influence of Sequential Nitrogen Substitution on the Redox Properties of Bis(thiazolylidene)hydrazine and on the Charge Transfer of TCNQ Complexes

Charge transfer complexes and cation radical salts of azino-diselenadiazafulvalene

“…1). This organization is reminiscent of what we previously observed with (azino-dithiadiazafulvalenes)(TCNQ) complexes [5]. Analysis of the bond lengths in the TCNQ skeleton shows that they are essentially similar to those reported for the neutral TCNQ [10] (see Table 2), confirming that the complex (1)(TCNQ) is neutral.…”

“…The synthesis of N,N 0 -bis(benzo-3H-selenazol-2-ylidene)-hydrazine (azino-DSeDAF) 1 was performed by using salt 3 in the presence of NEt 3 and half an equivalent of hydrazine hydrate, affording azinoDSeDAF 1 in 55% yield. For the synthesis of unsymmetrical azino donors, containing one selenazole and one thiazole cores, we first prepared the appropriate heterocyclic hydrazones 4 and 5 [5] which are consequently coupled with selenazolium salt 3 in basic medium as depicted in Scheme 1. Indeed, the reaction between selenazolium salt 3 and 3-methyl-3H-benzothiazol-2-one hydrazone 4 [7] in MeCN/EtOH in the presence of NEt 3 afforded azinodibenzoselenathiadiazafulvalene (azino-dibenzoSeTDAF) 6 in 70% yield.…”

“…Within these azino derivatives, Hünig et al, showed that the three oxidation levels of this system could be isolated, but except one further work on conductivity measurements, no other studies were performed on these donors such as structural or EPR [4]. In an earlier study we examined the potential of azino-dithiadiazafulvalenes as precursors of charge transfer complexes in the presence of TCNQ [5].…”

1,2-Bis(1,3-dithiol-2-ylidene)hydrazine

“…For general background, see: Yoshita et al (1983); Moore et al, (1998); Taniguchi et al (2003). For useful properties of related compounds, see: Andreu et al, (2004); Guerin et al (2002). For the synthesis of the starting material, 2-methylthio-1,3-dithiolium iodide, see: Challenger et al (1953).…”

“…Within the field of molecular conductors, tetrathiafulvalene and its π-derivatives have played a leading role in the formation of organic charge-transfer complexes (Yoshita et al 1983;Moore et al, 1998;Taniguchi et al 2003). One of the important strategies for the molecular design is to incorporate the nitrogen atom instead of carbon atoms to the conjugated spacer to modulate electron-donating properties (Andreu et al, 2004;Guerin et al, 2002). As a π-extended tetrathiafulvalene, we synthesized the title compound by incorporation an azino spacer between two 1,3-dithiole units.…”