Tetrathiafulvalene (TTF) is well known in the discipline of materials chemistry for its
excellent electron donating properties. For decades, considerable efforts have been made to
design and synthesize novel -extended analogues of TTF (ex-TTFs) in order to exploit the
application in electronic and optoelectronic devices. Of the vast array of ex-TTFs known so far,
the class of vinylogous derivatives of TTF (TTFVs) has attracted the interest of many research
groups. TTFVs are ideal candidates for organic-based electronics as they have a low band gap
and rich electroactivity. This has posed the need to further investigate the interesting and
inherently peculiar nature of TTFV; in particular, the structure-property relationship that exists
with aryl based TTFVs has been a focus of this thesis work. Through the use of aryl substituents
conformational control of TTFV has been demonstrated. The use of a 1-naphthyl substituent
allowed a neutral TTFV to take an unprecedented trans conformation as a result of significant
allylic strain. Additionally, an unprecedented tricyclic S-containing heterocycle was produced
via ortho brominated aryl substituents. Finally, a group of alkynylated phenyl-TTFVs were
synthesized and characterized. The molecular properties of all the new TTFV and related
compounds have been studied by single crystal X-ray diffraction, UV-Vis absorption
spectroscopy, and cyclic voltammetry
