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Issue 6, 2016
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The Raman fingerprint of cyclic conjugation: the case of the stabilization of cations and dications in cycloparaphenylenes

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Abstract

Radical cations and dications of [n]CPP from n = 5 to n = 12 have been studied by Raman spectroscopy and density functional theory. Small [n]CPP dications owe their stability to the closed-shell electronic structure imposed by cyclic conjugation surpassing the destabilizing effect of ring strain and of the electron deficiency of the charged states. Large [n]CPP dications mitigate cyclic strain by forming diradicals. The Raman spectra reflect the balance among cyclic conjugation, cyclic strain and biradicaloid stabilization by finding an unexpected turning point in the frequency behavior of the G vibrational modes as a function of size. These Raman data represent the vibrational fingerprint of this rare form of conjugation which is central to stabilize both cations and dications of [n]CPP macrocycles.

Graphical abstract: The Raman fingerprint of cyclic conjugation: the case of the stabilization of cations and dications in cycloparaphenylenes

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Publication details

The article was received on 18 Feb 2016, accepted on 06 Apr 2016 and first published on 06 Apr 2016


Article type: Edge Article
DOI: 10.1039/C6SC00765A
Citation: Chem. Sci., 2016,7, 3494-3499
  • Open access: Creative Commons BY license
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    The Raman fingerprint of cyclic conjugation: the case of the stabilization of cations and dications in cycloparaphenylenes

    M. P. Alvarez, M. C. Ruiz Delgado, M. Taravillo, V. G. Baonza, J. T. López Navarrete, P. Evans, R. Jasti, S. Yamago, M. Kertesz and J. Casado, Chem. Sci., 2016, 7, 3494
    DOI: 10.1039/C6SC00765A

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