Please use this identifier to cite or link to this item: https://doi.org/10.1021/jp030254h
Title: Ab initio studies of borazine and benzene cyclacenes and their fluoro-substituted derivatives
Authors: Loh, K.P. 
Yang, S.W. 
Soon, J.M.
Zhang, H. 
Wu, P.
Issue Date: 21-Jul-2003
Citation: Loh, K.P., Yang, S.W., Soon, J.M., Zhang, H., Wu, P. (2003-07-21). Ab initio studies of borazine and benzene cyclacenes and their fluoro-substituted derivatives. Journal of Physical Chemistry A 107 (29) : 5555-5560. ScholarBank@NUS Repository. https://doi.org/10.1021/jp030254h
Abstract: We have performed unrestricted density functional theory calculations for the borazine and benzene cyclacene systems to obtain insights into their structural and electronic properties as a function of the size of the cyclacene. The frontier molecular orbital gap, ΔEgap, in borazine cyclacene increases steadily with the number of rings, n, and stabilizes at ∼6.7 eV for n > 9, in contrast to the benzene cyclacene system where the gap decreases and approaches 1.13 eV for n > 8. For borazine cyclacene, the top and bottom trannulenes in the rings are structurally different. A stronger delocalization of π electrons in the boron-apexed trannulene compared to the nitrogen-apexed trannulene was discovered. For the carbon cyclacene, we observed alternation in both ΔEgap and the bond distances as the number of electrons in the trannulene chains alternate between 4k and 4k + 2. The effect of fluorine substitution on boron atoms in the borazine cyclacene increases the bonding energy and ΔEgap, whereas substitution on nitrogen atoms results in the opposite. A special π-type interaction between the fluorine lone-pair p electrons and the B-N-B σ-bonding framework results in special enhancement in the stability of the F-B substituted systems. F substitution on carbon cyclacene increases the ΔEgap when n is even but decreases ΔEgap when n is odd.
Source Title: Journal of Physical Chemistry A
URI: http://scholarbank.nus.edu.sg/handle/10635/114985
ISSN: 10895639
DOI: 10.1021/jp030254h
Appears in Collections:Staff Publications

Show full item record
Files in This Item:
There are no files associated with this item.

SCOPUSTM   
Citations

22
checked on Sep 21, 2018

WEB OF SCIENCETM
Citations

23
checked on Sep 11, 2018

Page view(s)

71
checked on Sep 21, 2018

Google ScholarTM

Check

Altmetric


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.