Very-low-lying electronic states result from n --> pi excitations in open-shell annulenes, annelated with
Xin Zhou1, David A Hrovat, Weston Thatcher Borden
1Department of Chemistry, University of North Texas, P.O. Box 305070, Denton, Texas 76203-5070, USA.
Abstract:
UB3LYP/6-31G* calculations find that alpha-dicarbonyl-annelated cyclopentadienyl radical 1 has a sigma ground state, which is formed by excitation of an electron from the in-phase combination of carbonyl lone-pair orbitals into the singly occupied pi orbital. Similarly, tetrakis-annelated cyclooctatetraene 3 is calculated to have very-low-lying singlet and triplet excited states, which result from excitations of electrons from the b1g combination of lone pair orbitals into the empty pi nonbonding MO of the COT ring.
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