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Reference: Parkinson, P, Kondratuk, DV, Menelaou, C et al., (2014). Chromophores in molecular nanorings: when is a ring a ring?. The journal of physical chemistry letters, 5 (24), 4356-4361.Citable link to this page:


Chromophores in molecular nanorings: when is a ring a ring?

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.

Peer Review status:Peer reviewedPublication status:PublishedVersion:Publisher's version Funder: Engineering and Physical Sciences Research Council   Notes:Copyright © 2014 American Chemical Society. ACS AuthorChoice - This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.

Bibliographic Details

Publisher: American Chemical Society

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Journal: The journal of physical chemistry letterssee more from them

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Issue Date: 2014


Urn: uuid:14c14078-a950-4821-b500-6d968c316c12

Source identifier: 500740

Eissn: 1948-7185


Issn: 1948-7185 Item Description

Type: Journal article;

Language: eng

Version: Publisher's versionKeywords: chromophores conjugation nanoring ultrafast spectroscopy spectroscopy photochemistry excited states Tiny URL: pubs:500740


Autor: Parkinson, P - institutionUniversity of Oxford Oxford, MPLS, Physics, Condensed Matter Physics - - - Kondratuk, DV - institutionU



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