We report a comparative study of the optoelectronic properties of small acenes (benzene, anthracene, and pentacene) and their bis-triisopropylsilylethynyl (TIPS) functionalized counterparts. We computed the fundamental gap using density functional theory (DFT) in the framework of the Delta SCF scheme, and the optical absorption spectra by means of time-dependent DFT. Upon TIPS functionalization we observed a lowering of the ionization energy and a rise of the electron affinity; we consequently predict a systematic reduction of the fundamental electronic gap which decreases from similar to 40% for benzene to similar to 16% for pentacene. This trend is reflected in the computed optical absorption spectra: for all TIPS-molecules the onset of absorption is red-shifted as compared to their plain precursors. In the case of TIPS-pentacene, in particular, the computed spectrum agrees with the available experimental data. (c) 2013 Elsevier B.V. All rights reserved.