Thermodynamics and Kinetics of Formation of Intramolecular Naphthalene Dimer Radical Cation Studied by Near-IR Transient Absorption Spectroscopy

Thermodynamics and kinetics for formation of an intramolecular dimer radical cation of a series of α,ω-di(2-naphthyl)alkanes in solutions were quantitatively investigated by near-IR transient absorption spectroscopy, which allows one to observe dimer radical cations directly. The standard enthalpy (−ΔH°) for the formation of the intramolecular dimer radical cation increased as the chain length between the two naphthyl moieties increased, and was smaller than that of the intermolecular dimer radical cation of 2-ethylnaphthalene. This shows that −ΔH° depends on the strain required for the chain to form the ring-closure configuration. Destabilization due to repulsion between the two naphthyl moieties in the intramolecular dimer radical cation was evaluated to be ca. 20 kJ mol−1. This value is smaller than that of the naphthalene excimer, indicating that the separation distance and/or the overlap between the two naphthyl moieties are not as restricted as those of the excimer. The activation energy for the formation of the intramolecular dimer radical cation was comparable to the energy for local motions of a few methylene units linking the two naphthalene moieties.