Influence of substituents of Perylenebisimides on the surface energy and wettability: A systematic structure–property relationship analysis

Abstract

This paper seeks to elucidate the influence on the surface wettability of a variety of substituents located in different positions of the perylene bisimide (PBI) core (ortho versus imide) with distinct electron-donor or -withdrawing character and diverse steric demand, using for this more than 20 planar PBIs. The correlation between the polarity of the individual functional group on the PBI and the surface wettability has been addressed by means of substituent descriptors in terms of Hansch-Fujita π parameter, Hammett σmeta and σpara constants, and steric parameters (Taft-Dubois Es’ and Charton υ). With these parameters, a quantitative structure–property relationship (QSPR) analysis has been performed using multivariable linear regression (MLR) fittings. The relationship of Surface Energy, determined by the static contact angle method with three different solvents, to structural properties of PBIs is described. As well, the polar and dispersive contributions have been determined. For planar PBIs, a predominant influence of the substituents in the imide position on the surface wettability has been found despite of the electronic nature and steric hindrance of the substituents simultaneously located in ortho positions. This effect is more pronounced with the longer alkyl substituents at the imide position. This study paves the way for a rational chromophore design considering the on surface behavior, which will ultimately condition the contact and thus their performance in optoelectronic devices.