title: Breaking the Symmetry in Molecular Nanorings.
abstract: Because of their unique electronic properties, cyclic molecular structures ranging from benzene to natural light-harvesting complexes have received much attention. Rigid π-conjugated templated porphyrin nanorings serve as excellent model systems here because they possess well-defined structures that can readily be controlled and because they support highly delocalized excitations. In this study, we have deliberately modified a series of six-porphyrin nanorings to examine the impact of lowering the rotational symmetry on their photophysical properties. We reveal that as symmetry distortions increase in severity along the series of structures, spectral changes and an enhancement of radiative emission strength occur, which derive from a transfer of oscillator strength into the lowest (k = 0) state. We find that concomitantly, the degeneracy of the dipole-allowed first excited (k = ±1) state is lifted, leading to an ultrafast polarization switching effect in the emission from strongly symmetry-broken nanorings.
authors.affiliation: Department of Physics, Clarendon Laboratory, University of Oxford , Parks Road, Oxford OX1 3PU, United Kingdom.
authors.forename: Juliane Q
authors.initials: JQ
authors.lastname: Gong
authors.affiliation: Department of Chemistry, Chemistry Research Laboratory, University of Oxford , Oxford OX1 3TA, United Kingdom.
authors.forename: Ludovic
authors.initials: L
authors.lastname: Favereau
authors.affiliation: Department of Chemistry, Chemistry Research Laboratory, University of Oxford , Oxford OX1 3TA, United Kingdom.
authors.forename: Harry L
authors.initials: HL
authors.lastname: Anderson
authors.affiliation: Department of Physics, Clarendon Laboratory, University of Oxford , Parks Road, Oxford OX1 3PU, United Kingdom.
authors.forename: Laura M
authors.initials: LM
authors.lastname: Herz