Revealing the way of self-complementary dimerization for a shape-persistent macrocycle using density functional theory calculations.
A preferred geometry of a planar shape-persistent dimeric macrocycle with diacetylene-linked alternating hexylbenzene and perfluorobenzene rings is revealed by resolving its three-dimensional spatial energy profile using density functional theory calculations. The resulting dimer exhibits a face-to-face geometry with about 51.5 degrees rotational off-set around the principal axis and an intermolecular distance of about 3.91 A. The calculated intermolecular interaction energy and the 1H NMR chemical shifts of the exo- and endo-annular protons of the predicted dimer agree very well with the recent experimental data. More importantly, the current study resolves the ambiguity observed in the experiment pertaining to how the dimer would form, and provides insight for predicting the geometry of similar dimeric macrocycles or other pi-pi interacting systems.
Institute of High Performance Computing, The Capricorn, Singapore 117528, Singapore.
Man-Fai
MF
Ng
Shuo-Wang
SW
Yang