Role of the \u3c0\u3c3* State in Molecular Photophysics

摘要

Photosynthesis, which depends on light-driven energy and electron transfer in assemblies of porphyrins, chlorophylls, and carotenoids, is just one example of the many complex natural systems of photobiology. A fuller understanding of the spectroscopy and photophysics of simple aromatic molecules is central to elucidating photochemical processes in the more sophisticated assemblies of photobiology. Moreover, developing a better grasp of the photophysics of simple aromatic molecules will also enhance our ability to create and improve practical applications in photochemical energy conversion, molecular nanophotonics, and molecular electronics. In this Account, we present a concerted experimental and theoretical study of aromatic ethynes, aromatic nitriles, and fluorinated benzenes, illustrating the important roles that the low-lying \u3c0\u3c3* state plays in the electronic relaxation of these aromatic compounds. Diphenylacetylene, 4-dialkylaminobenzonitriles, 4-dialkylaminobenzethynes, and fluorinated benzenes exhibit fluorescence that strongly quenches as the excitation energy is increased for gas-phase systems and at elevated temperatures in solution. Much of this interesting photophysical behavior can be attributed to the presence of a dark intermediate state that crosses the fluorescent \u3c0\u3c0* state. Our quantum chemistry calculations, as well as time-resolved laser spectroscopies, indicate that this dark intermediate state is the \u3c0\u3c3* state that arises from the promotion of an electron from the \u3c0 orbital of the phenyl ring to the \u3c3* orbital localized in the CtX group (where X is CH and N) or on the CsX group (where X is a halogen). These crossings not only lead to the strong excitation energy and temperature dependence of fluorescence but also induce highly interesting \u3c0\u3c3*-mediated intramolecular charge transfer in 4-dialkylaminobenzonitriles. Most previous studies on the excited-state dynamics of organic molecules have examined aromatic hydrocarbons, nitrogen heterocycles, aromatic carbonyl compounds, and polyenes, which have low-lying excited states of \u3c0\u3c0* character (hydrocarbons and polyenes) or n\u3c0* and \u3c0\u3c0* character (carbonyls and N-heterocycles). These studies have revealed important involvement of selection rules (promoting vibrational modes and spin-orbit coupling) and Franck-Condon factors for radiationless transitions, which have important effects on photophysical properties. The recent experimental and time-dependent density functional theory (TDDFT) calculations of aromatic ethynes, nitriles, and perfluorinated benzenes described in this Account demonstrate the importance of the bound excited state of a \u3c0\u3c3* configuration in these molecules.