Effect of Facial Encumbrance on Excimer Formation and Charge Resonance Stabilization in Model Bichromophoric Assemblies

Abstract

Excimer formation and charge resonance stabilization in covalently linked bichromophoric systems with flexible spacers are important processes relevant to biochemistry and functional materials. Requiring a π-stacked cofacial arrangement of a pair of aromatic molecules at a van der Waals contact, the underlying geometrical reorganization that accompanies these events continues to be debated. Here we use a variety of methods including two-color resonant two-photon ionization spectroscopy (2CR2PI), ion yield measurements, hole-burning spectroscopy (HB), and laser-induced fluorescence (LIF) excitation and emission spectroscopy to compare the gas-phase spectroscopy and dynamics of the van der Waals dimers of fluorene, 9-methylfluorene (MF), and 9,9′-dimethylfluorene (F1). The goal of this work is to probe the influence of methyl substitution on the dynamics of excimer formation and charge resonance (CR) stabilization. The fluorene dimer, (F)2, displays lifetime broadened electronic spectra and the dominance of...