Synthesis, Structure, Thermal Behavior and cis/trans Isomerization of 2,2′-(EMe3)2 (E = C, Si, Ge, Sn) Substituted Azobenzenes

Abstract

The synthesis of a series of 2,2′-bis(trimethyltetrel) azobenzenes is reported, evaluating the different synthetic approaches that different group 14 element substituents individually require. The synthetic access to the carbon substituted congener is very different from the heavier tetrels, in that the key step is the formation of the N=N bond in azobenzene, rather than the azobenzene-C bond. Sn could be introduced with a cross-coupling route, whereas the Si and Ge congeners were prepared by a stannylation-lithiation-electrophilic quenching sequence. Iodo-lithium exchange was also a possible route to obtain the dilithiated species, which can be attributed to the chelating effect of the nitrogen atoms. However, the organo-lead species could not be obtained via these routes. The resulting structures were fully characterized (NMR, FTIR, HRMS and XRD). Furthermore, their thermal properties (TGA and DSC) and their photoswitching behavior in solution (UV-VIS & NMR experiments) were investigated and compared for the different tetrels (C, Si, Ge, Sn).