Issue 17, 2016

From linear to cyclic oligoparaphenylenes: electronic and molecular changes traced in the vibrational Raman spectra and reformulation of the bond length alternation pattern

Abstract

Cyclic paraphenylenes, [n]CPPs, and linear paraphenylenes, [n]LPPs, formed by n benzenes, are investigated by Raman spectroscopy for n = 5 to 12 and density functional theory (DFT) for n = 4 to 20. The information on the experimental Raman frequencies and intensities, combined with DFT computations and reported X-ray diffraction structures, provides a consistent interpretation of the Raman spectra and allows establishing relevant structure–property trends. Structural and electronic effects such as benzene ring bending, inter-ring torsions, π-conjugation (aromaticity) and orbital energy gaps as a function of the linear elongation in [n]LPPs versus the macrocyclic curvature in [n]CPPs and of the molecular size (i.e., polymer limit) are systematically analyzed on the basis of the vibrational Raman properties. Changes in the BLA as an indicator of the degree of quinonoid character are analyzed and linked to the Effective Conjugation Coordinate (ECC) model. The BLA patterns involved in twisted and non-twisted conformations and in different species (bipolarons, quinonoid tautomers, and ECC active modes) are compared and their differences are discussed. This paper offers a unified interpretation of structural and electronic aspects in relation to the evolution from linear 1D π-systems to cyclic 2D structures.

Graphical abstract: From linear to cyclic oligoparaphenylenes: electronic and molecular changes traced in the vibrational Raman spectra and reformulation of the bond length alternation pattern

Supplementary files

Article information

Article type
Paper
Submitted
14 Sep 2015
Accepted
18 Nov 2015
First published
18 Nov 2015

Phys. Chem. Chem. Phys., 2016,18, 11683-11692

Author version available

From linear to cyclic oligoparaphenylenes: electronic and molecular changes traced in the vibrational Raman spectra and reformulation of the bond length alternation pattern

M. Peña-Alvarez, L. Qiu, M. Taravillo, V. G. Baonza, M. C. R. Delgado, S. Yamago, R. Jasti, J. T. L. Navarrete, J. Casado and M. Kertesz, Phys. Chem. Chem. Phys., 2016, 18, 11683 DOI: 10.1039/C5CP05500H

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