The goal of this brief partly review paper is to summarize the results of
the works published over the last few years
regarding the origin of the out-of-plane distortions (puckering) of
heterocyclic compounds. In all the papers devoted to this problem, it is shown that the
instability of planar configurations of heterocyclic molecules leading to
symmetry breaking and distortions is induced by the pseudo Jahn-Teller effect
(PJTE). Special attention in this work is paid to the mechanism of suppression
and enhancement of the PJTE distortions of heterocycles by oxidation,
reduction, and chemical substitutions. It is demonstrated that oxidation of
1,4-dithiine containing compounds leads to suppression of
the PJTE and to restoration of their planar nuclear configurations. An example
of a dibenzo[1,2]dithiine molecule is used to demonstrate the mechanism of enhancement
of the PJTE by reduction. It is shown that the reduction of the neutral C12H8S2 molecule up to the dianion (C12H8S2)2- enhances the PJTE, followed by the S-S bond cleavage and significant structural
distortions of the system. The change of the PJTE by chemical substitutions,
accompanied either by puckering or by planarization of heterocyclic compounds,
is discussed using as examples 1,4-ditinine and its S-oxygenated derivatives.
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Bersuker, I.B. (2001) Modern Aspects of the Jahn-Teller Effect Theory and Applications to Molecular Problems. Chemical Reviews, 101, 1067-1114. https://doi.org/10.1021/cr0004411
Bersuker, I.B. (2013) Pseudo Jahn-Teller Effect—A Two-State Paradigm in Formation, Deformation, and Transformation of Molecular Systems and Solids. Chemical Reviews, 113, 1351-1390. https://doi.org/10.1021/cr300279n
Ivanov, A.S., Bozhenko, K.V. and Boldyrev, A.I. (2012) On the Suppression Mechanism of the Pseudo-Jahn-Teller Effect in Middle E6 (E = P, As, Sb) Rings of Triple-Decker Sandwich Complexes. Inorganic Chemistry, 51, 8868-8872. https://doi.org/10.1021/ic300786w
Sergeeva, A.P. and Boldyrev, A.I. (2010) Flattening a Puckered Pentasilacyclopentadienide Ring by Suppression of the Pseudo Jahn-Teller Effect. Organometallics, 29, 3951-3954. https://doi.org/10.1021/om1006038
Jose, D. and Datta, A. (2012) Understanding of the Buckling Distortions in Silicene. The Journal of Physical Chemistry C, 116, 24639-24648. https://doi.org/10.1021/jp3084716
Ilkhani, A.R., Hermoso, W. and Bersuker, I.B. (2015) Pseudo Jahn-Teller Origin of Instability of Planar Configurations of Hexa-Heterocycles. Application to Compounds with C4X2 Skeletons (X = O, S, Se, Te). Chemical Physics, 460, 75-82.
Gorinchoy, N.N. and Bersuker, I.B. (2017) Pseudo Jahn-Teller Effect in Control and Rationalization of Chemical Transformations in Two-Dimensional Compounds. Journal of Physics: Conference Series, 833, 012010. https://doi.org/10.1088/1742-6596/833/1/012010
Bersuker, I.B. (2017) Manipulation of Structure and Properties of Two-Dimensional Systems Employing the Pseudo Jahn-Teller Effect. FlatChem, 6, 11-27. https://doi.org/10.1016/j.flatc.2017.10.001
Pratik, S.M., Chowdhury, C., Bhattacharjee, R., Jahiruddin, Sk. and Datta, A. (2015) Pseudo Jahn-Teller Distortion for a Tricyclic Carbon Sulfide (C6S8) and Its Suppression in S-Oxygenated Dithiine (C4H4(SO2)2). Chemical Physics, 460, 101-105. https://doi.org/10.1016/j.chemphys.2015.04.009
Pratik, S.M. and Datta, A. (2015) 1,4-Dithiine-Puckered in the Gas Phase But Planar in Crystals: Role of Cooperativity. The Journal of Physical Chemistry C, 119, 15770-15776. https://doi.org/10.1021/acs.jpcc.5b04908
Ilkhani, A.R. (2015) Pseudo Jahn-Teller Origin of Twisting in 3,6-Pyridazinedione Derivatives; N2C4H2Y2Z2 (Y = O, S, Se, Z = H, F, Cl, Br) Compounds. Journal of Theoretical and Computational Chemistry, 14, Article ID: 1550045. https://doi.org/10.1142/S0219633615500455
Ilkhani, A.R., Gorinchoy, N.N. and Bersuker, I.B. (2015) Pseudo Jahn-Teller Effect in Distortion and Restoration of Planar Configurations of Tetra-Heterocyclic 1,2-diazetes C2N2E4, E = H, F, Cl, Br. Chemical Physics, 460, 106-110. https://doi.org/10.1016/j.chemphys.2015.07.015
Ilkhani, A.R. (2017) The Symmetry Breaking Phenomenon in 1,2,3-Trioxolene and C2Y3Z2 (Z = O, S, Se, Te, Z = H, F) Compounds: A Pseudo Jahn-Teller Origin Study. Química Nova, 40, 491-495. https://doi.org/10.21577/0100-4042.20170029
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Ilkhani, A.R. (2017) Pseudo Jahn-Teller Effect in Oxepin, Azepin, and Their Halogen Substituted Derivatives. Russian Journal of Physical Chemistry A, 9, 1743-1751. https://doi.org/10.1134/S0036024417090035
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Vessally, E. (2008) DFT Calculations on 1,4-dithiine and S-oxygenated Derivatives. Bulletin of the Chemical Society of Ethiopia, 22, 465-468. https://doi.org/10.4314/bcse.v22i3.61259
