Journal of Physical Chemistry A, Vol.124, No.26, 5408-5414, 2020
Mobius and Huckel Cyclacenes with Dewar and Ladenburg Defects
Cyclacene nanobelts have not been synthesized in over 60 years and remain one of the last unsynthesized building blocks of carbon nanotubes. Recent work has predicted that Huckel-cyclacenes containing Dewar benzenoid ring isomers are the most stable isomeric forms for several of the smaller sizes of cyclacene belts. Here, we give a more complete picture of the isomers that are possible within these nanobelt systems by simulating embedded Ladenburg (prismane) benzenoid rings in Huckel-[n]cyclacenes (n = 5-14) and embedded Dewar benzenoid rings in twisted Mobius-[n]cyclacenes (n = 9-14). The Mobius-[9]cyclacene isomer containing one Dewar benzenoid defect and the Huckel-[5]cyclacene isomer containing two maximally spaced Ladenburg benzenoid defects are found to be more stable than their conventional Kekule benzenoid ring counterparts. The isomers that contain Dewar and Ladenburg benzenoid rings have larger electronic singlet-triplet energy gaps and lower polyradical character when compared with the conventional isomers.