Role of peripheral substitution on electronics and self-assembly of discotic semiconductors: The case of diazatruxenone

Abstract

In this paper we present two sets of diazatruxenones functionalized at the 3,8 or 2,7 positions with two phenyl rings substituted at the para positions with groups of different electronic nature. With the aim to shed light on the role of the positional isomeric effect and of the electronic nature of the attached peripheral substituents on the final properties of these systems, we have performed a joint experimental and theoretical investigation linking thermal analysis, UV–Vis spectroscopy, electrochemistry and SCLC measurements with DFT calculations. The donor–acceptor character of these molecules not only confers them an interesting amphoteric redox behaviour but also creates a significant in-plane dipole moment. We have found that the different functionalization has only a slight impact on the electronic properties of these systems but exerts a significant influence on the strength and directionality of their dipole moment with strong implications in their self-assembly. Particularly, derivatives functionalized with electron acceptors, present the highest dipole moments within the series and form stable columnar mesophases, probably driven by the antiparallel dipole–dipole arrangement of neighbouring molecules. DFT calculations confirms that cofacially stacked dimers with their dipoles opposed allow for efficient electronic couplings helping to rationalize the favourable hole mobilities determined for the 3,8-disubstituted diazatruxenones with electron-acceptor groups by means of the space charge–limited current technique.