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The resonance of cation and anion radicals with multiple conjugated bonds

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Abstract

This work describes a computational study of the electronic structure of anion and cation radicals of some conjugated systems—buta-1,3-diyne, hexa-1,3,5-triyne, buta-1,3-diene, and hexa-1,3,5-triene. The main purpose was to investigate how the gain or loss of one electron affected the geometry and, electron and spin densities. The NBO, QTAIM, ELF, and LMO-EDA methods helped to study the electronic structure of the target compounds and their radicals. Several methods indicate an increased electronic delocalization upon ionization. The unpaired electron is preferentially localized at the terminal carbon atoms in radicals. The calculated isodesmic and homodesmotic bond separation reactions indicated that disruption of the conjugation system prompted higher energy at the radicals as compared with neutral molecules.

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Acknowledgments

The authors thank the Brazilian agencies CAPES/PROAP, CNPq, (Grant 481560/2010-6), and São Paulo Research Foundation (FAPESP) (Grant 2008/02677-0) for financial support. SEG thanks CNPq for a research fellowship (Grant 304447/2010-2). RPO thanks FAPESP for undergraduate and PhD fellowships (Grants 2009/08712-4 and 2011/20351-7). We also acknowledge Dr. Cynthia M. C. Prado Manso for revising the manuscript and MSc. Ali Faez Taha for technical assistance.

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  1. Departamento de Química, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Ribeirão Preto, SP, 14040-901, Brazil

    Renato Pereira Orenha, Ricardo Vessecchi & Sérgio E. Galembeck

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  1. Renato Pereira Orenha
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  2. Ricardo Vessecchi
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  3. Sérgio E. Galembeck
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Correspondence to Sérgio E. Galembeck.

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Orenha, R.P., Vessecchi, R. & Galembeck, S.E. The resonance of cation and anion radicals with multiple conjugated bonds. Struct Chem 26, 365–373 (2015). https://doi.org/10.1007/s11224-014-0490-7

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