polyhedral phenylacetylenes the interplay of aromaticity and antiaromaticity in convex graphyne substructures多面苯乙炔芳香性的相互作用和antiaromaticity凸graphyne子结构.pdf

Symmetry 2009, 1, 226-239; doi:10.3390/sym1020226 OPEN ACCESS symmetry ISSN 2073-8994 /journal/symmetry Article Polyhedral Phenylacetylenes: The Interplay of Aromaticity and Antiaromaticity in Convex Graphyne Substructures Daniel Sebastiani and Matt A. Parker Physics Department, Free University Berlin, Arnimallee 14, 14195 Berlin, Germany MPI Polymer Research, Ackermannweg 10, 55128 Mainz, Germany Department of Chemistry and Biochemistry, San Diego State University, San Diego, CA 92182, USA Author to whom correspondence should be addressed; E-Mail: daniel.sebastiani@fu-berlin.de; Tel.: +49-30-838-53037; Fax: +49-30-838-56046. Received: 10 November 2009 / Accepted: 27 November 2009 / Published: 11 December 2009 Abstract: We have studied a series of bridged phenylacetylene macrocycles with topologies based on Platonic and Archimedean polyhedra, using density functional calculations to determine both their molecular structure and their electronic response to external magnetic fields (NICS maps). We are able to elucidate the interplay of aromaticity and anti-aromaticity as a function of structural parameters, in particular the symmetry properties of the intramolecular bond connectivities, in these compounds. Keywords: aromaticity; nucleus independent chemical shifts; density functional theory calculations; phenylacetylene; graphyne Classification: PACS 31.15.A-, 33.15.Bh, 31.15.E-, 33.25.+k 1. Introduction Graphite is the well-known lowest-energy unsaturated allotrope of carbon, consisting en