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Parkinson P, Kondratuk DV, Menelaou C, et al. Chromophores in Molecular Nanorings: When Is a Ring a Ring?. J Phys Chem Lett. 2014;5(24):4356-61doi: 10.1021/jz5022153.
Parkinson, P., Kondratuk, D. V., Menelaou, C., Gong, J. Q., Anderson, H. L., & Herz, L. M. (2014). Chromophores in Molecular Nanorings: When Is a Ring a Ring?. The journal of physical chemistry letters, 5(24), 4356-61. https://doi.org/10.1021/jz5022153
Parkinson, Patrick, et al. "Chromophores in Molecular Nanorings: When Is a Ring a Ring?." The journal of physical chemistry letters vol. 5,24 (2014): 4356-61. doi: https://doi.org/10.1021/jz5022153
Parkinson P, Kondratuk DV, Menelaou C, Gong JQ, Anderson HL, Herz LM. Chromophores in Molecular Nanorings: When Is a Ring a Ring?. J Phys Chem Lett. 2014 Dec 18;5(24):4356-61. doi: 10.1021/jz5022153. Epub 2014 Dec 08. PMID: 26273987.
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J Phys Chem Lett. 2014 Dec 18;5(24):4356-61. doi: 10.1021/jz5022153. Epub 2014 Dec 08.

Chromophores in Molecular Nanorings: When Is a Ring a Ring?.

The journal of physical chemistry letters

Patrick Parkinson, Dmitry V Kondratuk, Christopher Menelaou, Juliane Q Gong, Harry L Anderson, Laura M Herz

Affiliations

  1. †Department of Physics, University of Oxford, Clarendon Laboratory, Parks Road, Oxford OX1 3PU, United Kingdom.
  2. ‡Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford OX1 3TA, United Kingdom.

PMID: 26273987 DOI: 10.1021/jz5022153

Abstract

The topology of a conjugated molecule plays a significant role in controlling both the electronic properties and the conformational manifold that the molecule may explore. Fully π-conjugated molecular nanorings are of particular interest, as their lowest electronic transition may be strongly suppressed as a result of symmetry constraints. In contrast, the simple Kasha model predicts an enhancement in the radiative rate for corresponding linear oligomers. Here we investigate such effects in linear and cyclic conjugated molecules containing between 6 and 42 butadiyne-linked porphyrin units (corresponding to 600 C-C bonds) as pure monodisperse oligomers. We demonstrate that as the diameter of the nanorings increases beyond ∼10 nm, its electronic properties tend toward those of a similarly sized linear molecule as a result of excitation localization on a subsegment of the ring. However, significant differences persist in the nature of the emitting dipole polarization even beyond this limit, arising from variations in molecular curvature and conformation.

Keywords: chromophores; conjugation; nanoring; ultrafast spectroscopy

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