Journal article

Publication year: 2009

Pages: 11750-11757

Journal: The Journal of Physical Chemistry A

Volume number: 113

Issue number: 43

DOI Link: https://doi.org/10.1021/jp9028672

Publisher: American Chemical Society

Abstract: 

The relationship between the structures and electronic
ground state properties of non-Kekulé-type N-substituted m-phenyleneswas
studied utilizing density functional theory (DFT), with the aim of determining
the factors that lead to ground state triplet diradicals. AtB3LYP/6-311G(d,p)//B3LYP/6-311G(d,p)
we identified octahydropyridoquinoline with an exceptionally large
singlet−triplet energy separation of +27.9 kcal mol⁻¹, in favor of
the triplet. The high-spin structures can readily be obtained by interruption
of the full cyclic π-delocalization that avoids cross-conjugation of the
nitrogen radical centers. Introduction of additional heteroatoms, on the other
hand, preferentially stabilizes thesinglet zwitterionic resonance contributors
in these systems. The identified diradicals show strong ferromagnetic exchange
interactions between two radical centers.

Harvard Citation style: Amiri, S. and Schreiner, P. (2009) Non-Kekulé N-Substituted m-Phenylenes: N-Centered Diradicals versus Zwitterions, The Journal of Physical Chemistry A, 113(43), pp. 11750-11757. https://doi.org/10.1021/jp9028672

APA Citation style: Amiri, S., & Schreiner, P. (2009). Non-Kekulé N-Substituted m-Phenylenes: N-Centered Diradicals versus Zwitterions. The Journal of Physical Chemistry A. 113(43), 11750-11757. https://doi.org/10.1021/jp9028672