Abstract
Understanding the electronic properties and electron transfer characteristics of functionalized oligoacenes is of great importance for the fabrication of organic electronic devices. Charge transfer parameters of bis-triisopropylsilylethynyl-substituted anthracene, tetracene, and pentacene have been investigated based on the analysis of their ionization energies and radical cation reorganization energies. High-resolution gas-phase photoelectron spectroscopy measurements and first-principles quantum-mechanical calculations at the density functional theory level have been performed. The results indicate that the ionization energies in the gas phase and the inner-sphere reorganization energies are sensitive to the number of fused rings and the substitution by the triisopropylsilylethynyl (TIPS) group. This TIPS functional group shifts the first ionization band of these molecules to lower energy in the gas phase due to mixing between the frontier occupied orbitals of the TIPS group with the highest occupied acene orbital. This mixing adds geometry modifications of the TIPS substituents to those of the acene core that occur with ionization, resulting in a near doubling of the reorganization energies with electron transfer for these molecules.