Document Type
Article
Original Publication Date
2010
Journal/Book/Conference Title
The Journal of Chemical Physics
Volume
133
DOI of Original Publication
1063/1.3488103
Date of Submission
October 2015
Abstract
Three-dimensional aromaticity is shown to play a role in the stability of deltahedral Zintl clusters and here we examine the connection between aromaticity and stability. In order to gain further insight, we have studied Zintl analogs comprised of bismuthdopedtin clusters with photoelectron spectroscopy and theoretical methods. To assign aromaticity, we examine the ring currents induced around the cage by using the nucleus independent chemical shift. In the current study, BiSn4− is a stable cluster and fits aromatic criteria, while BiSn5− is found to fit antiaromatic criteria and has reduced stability. The more stable clusters exhibit an aromatic character which originates from weakly interacting s-states and bonding orbitals parallel to the surface of the cluster, while nonbonding lone pairs perpendicular to the surface of the cluster account for antiaromaticity and reduced stability. The effect of three-dimensional aromaticity on the electronic structure does not result in degeneracies, so the resulting variations in stability are smaller than those seen in conventional aromaticity.
Rights
Clayborne, P. A., Gupta, U., Reber, A. C., et al. The applicability of three-dimensional aromaticity in BiSnn− Zintl analogues. The Journal of Chemical Physics 133, 134302 (2010). Copyright © 2010 AIP Publishing LLC.
Is Part Of
VCU Physics Publications
Comments
Originally published at http://dx.doi.org/10.1063/1.3488103