Electronic devices based on organic materials have been an area of intense research for the past several years. Pentacene, an oligoacene, is regarded as a benchmark due to its high charge carrier mobility. However it has poor solubilty, unoptimized π-overlap and is highly unstable. We have successfully demonstrated that peri-functionalization with trialkylsilyl ethynyl groups enhances the π-stacking, solubility and stability of pentacene and related compounds. TIPS pentacene exhibits both two dimensional (2D) 71-stacking and good solubilty in common organic solvents. However changing the solubilizing groups or functionalizing the acene core results in a disruption of the desired 2D 71-stacking. Molecules with one dimensional (1D) π-stacking have poorer mobility than those with 2D π-stacking and hence larger solubilizing groups are required to change the π-stacking to 2D. The emphasis of this paper is to show how small changes in substitution can disrupt π-stacking in these molecules and how one can achieve the desired π-stacking by careful selection of solubilzing groups.