Acenes and phenacenes in their lowest-lying triplet states. Does kinked remain more stable than straight?

Physical Chemistry Chemical Physics : PCCP
Ricardo Pino-RiosMiquel Solà

Abstract

The larger stability of phenacenes compared to their acene isomers in their ground states is attributed to the larger aromaticity of the former. To our knowledge the relative stability of acenes and phenacenes in their lowest-lying triplet states (T1) has not been discussed yet. Using unrestricted density functional theory calculations, our results show that for the smallest members of the series, acenes in their T1 states are more stable than the corresponding phenacenes. However, when the number of the rings (n) involved increases, the energy difference is reduced and for n > 12, phenacenes become more stable than acenes in their T1 states. To rationalize this trend, we analyze the aromaticity of acenes and phenacenes using a set of aromaticity descriptors. We find that in the T1 states of both acenes and phenacenes, the outer rings form aromatic Clar π-sextets. In acenes, delocalization of spin density in the central rings leads to the preferred formation of the largest antiaromatic diradical. Resonant structures in the form of antiaromatic diradical Baird π-octadectets and π-tetradectets are the major contributors, while the smaller ones, such as π-doublets and π-sextets, contribute the least. In phenacenes, structures with...Continue Reading

References

Nov 17, 2001·Chemical Reviews·T M Krygowski, M K Cyrański
Dec 26, 2001·Chemical Reviews·P R Schleyer
May 13, 2003·Chemistry : a European Journal·Chérif F MattaRichard F W Bader
Jun 17, 2004·Journal of the American Chemical Society·Michael BendikovFred Wudl
Jan 11, 2005·The Journal of Chemical Physics·Eduard MatitoMiquel Solà
Jul 14, 2006·The Journal of Physical Chemistry. a·David J Wolstenholme, T Stanley Cameron
Jul 26, 2006·The Journal of Physical Chemistry. a·Jordi PoaterMiquel Solà
Dec 15, 2006·Chemical Reviews·John E Anthony
Feb 10, 2007·The Journal of Organic Chemistry·Jordi PoaterF Matthias Bickelhaupt
May 24, 2007·The Journal of Physical Chemistry. a·Jordi PoaterMiquel Solà
Aug 4, 2007·Chemistry : a European Journal·A Martín PendásCarlo Gatti
Jun 13, 2008·Journal of Chemical Information and Modeling·Arkadiusz CiesielskiMichał K Cyrański
Aug 30, 2008·Physical Chemistry Chemical Physics : PCCP·Dmitry Yu Zubarev, Alexander I Boldyrev
Jul 10, 2009·The Journal of Physical Chemistry. a·Heike FlieglWim Klopper
Nov 5, 2011·Physical Chemistry Chemical Physics : PCCP·Ferran FeixasMiquel Solà
Dec 14, 2011·Journal of Computational Chemistry·Tian Lu, Feiwu Chen
Nov 24, 2012·Nature Chemistry·Henrik Ottosson
Jan 1, 2013·Frontiers in Chemistry·Miquel Solà
Mar 18, 2015·Physical Chemistry Chemical Physics : PCCP·Collins U Ibeji, Debashree Ghosh
Apr 11, 2015·Chemical Society Reviews·Ferran FeixasMiquel Solà
Jun 3, 2015·Chemical Society Reviews·Renana Gershoni-Poranne, Amnon Stanger
Aug 17, 2016·Proceedings of the National Academy of Sciences of the United States of America·Yang YangWeitao Yang
Oct 7, 2016·Nature Communications·Raffaello PapadakisHenrik Ottosson
Nov 24, 2017·Nature Chemistry·Won-Young ChaDongho Kim
Aug 2, 2018·The Journal of Physical Chemistry. a·Georges TrinquierJean-Paul Malrieu
Sep 27, 2019·Proceedings of the National Academy of Sciences of the United States of America·Chia-Hua WuJudy I-Chia Wu
Nov 12, 2019·The Journal of Physical Chemistry. a·Ricardo Pino-RiosWilliam Tiznado
Feb 19, 2020·The Journal of Organic Chemistry·Marija Baranac-Stojanović
May 5, 2020·ACS Omega·Jan Cz Dobrowolski, Grażyna Karpińska
May 29, 2020·Chemical Communications : Chem Comm·Zhili WenJudy I-Chia Wu
Dec 29, 2020·Chemistry : a European Journal·Christina Tönshoff, Holger F Bettinger

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