Theoretical study of
-
stacking interactions in substituted-coronene||cyclooctatetraene complexes: A system without direct electrostatic effects of substituents

Subject Areas : Journal of Physical & Theoretical Chemistry

Pouya  Karimi ¹ (Department of Chemistry, Faculty of Science, University of Zabol, P.O. Box 98613-35856, Zabol, Iran)

Received: 2015-08-06 Accepted : 2016-01-06 Published : 2016-03-01

Keywords: Coronene, cyclooctatetraene, -, stacking, NMR, Coupling constant,

Abstract :

Stability of the ;-; stacking interactions in the substituted-coronene||cyclooctatetraene complexes wasstudied using the computational quantum chemistry methods (where || denotes ;; stackinginteraction, and substituted-coronene is coronene which substituted with four similar X groups; X =OH, SH, H, F, CN, and NO). There are meaningful correlations between changes of geometricalparameters and topological properties of the electron charge densities at ring critical points due toformation of complexes and ;-; stacking binding energies. In these complexes both electronwithdrawingand electron-donating substituents lead to larger binding energies compared to X = H(unsubsitituetted-coronene||cyclooctatetraene complex).This finding was interpreted on the basis ofNMR data, especially spin-spin coupling constants between C atoms of cyclooctatetraene and C atomsat central rings of substituted-coronenes. Herein, relationships between the ;; stacking bindingenergy (-E) values and, through-space C-C spin-spin coupling constants (JC-C) in the substitutedcoronene||cyclooctatetraene complexes has been investigated in the complexes without directelectrostatic effects of substituents.