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Issue 2, 2011
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The optical activity of β,γ-enones in ground and excited states using circular dichroism and circularly polarized luminescence

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Abstract

The circularly polarized luminescence (CPL) and electronic circular dichroism (CD) spectroscopic parameters corresponding to the n ← π* and n → π* transitions, respectively, have been calculated for selected β,γ-enones using density functional theory. For the smallest β,γ-enone, (1R,4R)-bicyclo[2.2.1]hept-5-en-2-one (norbornenone), coupled-cluster calculations have also been carried out. The excited-state potential energy surface for three of the five enones studied reveals two minima with different C[double bond, length as m-dash]O⋯C[double bond, length as m-dash]C dihedral angles, and with rotatory strengths of opposite sign. The relative energies of the minima determine the sign of the CPL intensity, which may be the same or opposite as in the CD spectrum, in agreement with experimental data. The results obtained in this first computational study of CPL demonstrate its usefulness as an indicator of excited-state structures of chiral species.

Graphical abstract: The optical activity of β,γ-enones in ground and excited states using circular dichroism and circularly polarized luminescence

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Publication details

The article was received on 12 Jul 2010, accepted on 26 Aug 2010 and first published on 29 Oct 2010


Article type: Paper
DOI: 10.1039/C0CP01149E
Citation: Phys. Chem. Chem. Phys., 2011,13, 643-650
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    The optical activity of β,γ-enones in ground and excited states using circular dichroism and circularly polarized luminescence

    M. Pecul and K. Ruud, Phys. Chem. Chem. Phys., 2011, 13, 643
    DOI: 10.1039/C0CP01149E

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