Why 1,2‑quinone derivatives are more stable than their 2,3‑analogues?
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Data
2015-02-25Autor
Szatylowicz, Halina
Krygowski, Tadeusz M.
Solà, Miquel
Palusiak, Marcin
Dominikowska, Justyna
Stasyuk, Olga A.
Poater, Jordi
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In this work, we have studied the relative stability
of 1,2- and 2,3-quinones. While 1,2-quinones have
a closed-shell singlet ground state, the ground state for
the studied 2,3-isomers is open-shell singlet, except for
2,3-naphthaquinone that has a closed-shell singlet ground
state. In all cases, 1,2-quinones are more stable than their
2,3-counterparts. We analyzed the reasons for the higher
stability of the 1,2-isomers through energy decomposition
analysis in the framework of Kohn–Sham molecular orbital
theory. The results showed that we have to trace the origin
of 1,2-quinones’ enhanced stability to the more efficient
bonding in the π-electron system due to more favorable
overlap between the SOMOπ of the ·C4n−2H2n–CH·· and
··CH–CO–CO· fragments in the 1,2-arrangement. Furthermore,
whereas 1,2-quinones present a constant trend with their elongation for all analyzed properties (geometric,
energetic, and electronic), 2,3-quinone derivatives present a
substantial breaking in monotonicity.
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