caa a22 4500 605487669 CHVBK 20210128100451.0 cr unu---uuuuu 210128e20150301xx s 000 0 eng 10.1007/s00214-015-1635-5 doi (NATIONALLICENCE)springer-10.1007/s00214-015-1635-5 Why 1,2-quinone derivatives are more stable than their 2,3-analogues? [Elektronische Daten] [Halina Szatylowicz, Tadeusz Krygowski, Miquel Solà, Marcin Palusiak, Justyna Dominikowska, Olga Stasyuk, Jordi Poater] 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. The Author(s), 2015 Quinones nationallicence Benzenoids nationallicence Energy decomposition analysis nationallicence Aromaticity nationallicence Szatylowicz Halina Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664, Warsaw, Poland aut Krygowski Tadeusz Department of Chemistry, Warsaw University, Pasteura 1, 02-093, Warsaw, Poland aut Solà Miquel Departament de Química, Institut de Química Computacional i Catàlisi, Universitat de Girona, Campus de Montilivi, 17071, Girona, Catalonia, Spain aut Palusiak Marcin Department of Theoretical and Structural Chemistry, Faculty of Chemistry, University of Łódź, Pomorska 163/165, 90-236, Lodz, Poland aut Dominikowska Justyna Department of Theoretical and Structural Chemistry, Faculty of Chemistry, University of Łódź, Pomorska 163/165, 90-236, Lodz, Poland aut Stasyuk Olga Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664, Warsaw, Poland aut Poater Jordi Department of Theoretical Chemistry, Amsterdam Center for Multiscale Modeling, Vrije Universiteit, De Boelelaan 1083, 1081HV, Amsterdam, The Netherlands aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/3(2015-03-01), 1-14 1432-881X 134:3<1 2015 134 214 https://doi.org/10.1007/s00214-015-1635-5 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-015-1635-5 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Szatylowicz Halina Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664, Warsaw, Poland aut NATIONALLICENCE 700 1- Krygowski Tadeusz Department of Chemistry, Warsaw University, Pasteura 1, 02-093, Warsaw, Poland aut NATIONALLICENCE 700 1- Solà Miquel Departament de Química, Institut de Química Computacional i Catàlisi, Universitat de Girona, Campus de Montilivi, 17071, Girona, Catalonia, Spain aut NATIONALLICENCE 700 1- Palusiak Marcin Department of Theoretical and Structural Chemistry, Faculty of Chemistry, University of Łódź, Pomorska 163/165, 90-236, Lodz, Poland aut NATIONALLICENCE 700 1- Dominikowska Justyna Department of Theoretical and Structural Chemistry, Faculty of Chemistry, University of Łódź, Pomorska 163/165, 90-236, Lodz, Poland aut NATIONALLICENCE 700 1- Stasyuk Olga Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664, Warsaw, Poland aut NATIONALLICENCE 700 1- Poater Jordi Department of Theoretical Chemistry, Amsterdam Center for Multiscale Modeling, Vrije Universiteit, De Boelelaan 1083, 1081HV, Amsterdam, The Netherlands aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/3(2015-03-01), 1-14 1432-881X 134:3<1 2015 134 214