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Molecules 2018, 23(6), 1333; https://doi.org/10.3390/molecules23061333

Aromaticity as a Guiding Concept for Spectroscopic Features and Nonlinear Optical Properties of Porphyrinoids

1
Eenheid Algemene Chemie (ALGC), Vrije Universiteit Brussel (VUB), Pleinlaan 2, 1050 Brussels, Belgium
2
Laboratoire de Chimie Théorique, Unité de Chimie Physique Théorique et Structurale, University of Namur, Rue de Bruxelles 61, B-5000 Namur, Belgium
*
Author to whom correspondence should be addressed.
Academic Editors: Luis R. Domingo and Miquel Solà
Received: 5 March 2018 / Revised: 15 May 2018 / Accepted: 24 May 2018 / Published: 1 June 2018
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Abstract

With their versatile molecular topology and aromaticity, porphyrinoid systems combine remarkable chemistry with interesting photophysical properties and nonlinear optical properties. Hence, the field of application of porphyrinoids is very broad ranging from near-infrared dyes to opto-electronic materials. From previous experimental studies, aromaticity emerges as an important concept in determining the photophysical properties and two-photon absorption cross sections of porphyrinoids. Despite a considerable number of studies on porphyrinoids, few investigate the relationship between aromaticity, UV/vis absorption spectra and nonlinear properties. To assess such structure-property relationships, we performed a computational study focusing on a series of Hückel porphyrinoids to: (i) assess their (anti)aromatic character; (ii) determine the fingerprints of aromaticity on the UV/vis spectra; (iii) evaluate the role of aromaticity on the NLO properties. Using an extensive set of aromaticity descriptors based on energetic, magnetic, structural, reactivity and electronic criteria, the aromaticity of [4n+2] π-electron porphyrinoids was evidenced as was the antiaromaticity for [4n] π-electron systems. In agreement with previous studies, the absorption spectra of aromatic systems display more intense B and Q bands in comparison to their antiaromatic homologues. The nature of these absorption bands was analyzed in detail in terms of polarization, intensity, splitting and composition. Finally, quantities such as the average polarizability and its anisotropy were found to be larger in aromatic systems, whereas first and second hyperpolarizability are influenced by the interplay between aromaticity, planarity and molecular symmetry. To conclude, aromaticity dictates the photophysical properties in porphyrinoids, whereas it is not the only factor determining the magnitude of NLO properties. View Full-Text
Keywords: aromaticity; porphyrinoids; nonlinear optical properties; absorption spectra aromaticity; porphyrinoids; nonlinear optical properties; absorption spectra
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Woller, T.; Geerlings, P.; De Proft, F.; Champagne, B.; Alonso, M. Aromaticity as a Guiding Concept for Spectroscopic Features and Nonlinear Optical Properties of Porphyrinoids. Molecules 2018, 23, 1333.

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