computed nmr shielding effects over fused aromatic antiaromatic hydrocarbons在核磁共振屏蔽效应计算融合芳香antiaromatic碳氢化合物.pdfVIP

Symmetry 2010, 2, 418-436; doi:10.3390/sym2010418 OPEN ACCESS symmetry ISSN 2073-8994 /journal/symmetry Article Computed NMR Shielding Effects over Fused Aromatic / Antiaromatic Hydrocarbons Ned H. Martin *, Mathew R. Teague and Katherine H. Mills Department of Chemistry and Biochemistry, University of North Carolina Wilmington, 601 South College Road, Wilmington, NC 28403-5932, USA; E-Mails: mattrteague@ (M.R.T.); khm0327@ (K.H.M.) * Author to whom correspondence should be addressed; E-Mail: martinn@. Received: 14 January 2010; in revised form: 17 March 2010 / Accepted: 19 March 2010 / Published: 22 March 2010 Abstract: Through-space isotropic NMR shielding values of a perpendicular diatomic hydrogen probe moved in a 0.5 Å grid 2.5 Å above several polycyclic aromatic/antiaromatic ring and aromatic/aromatic hydrocarbons were computed with Gaussian 03 at the GIAO HF/6-31G(d,p) level. Combinations of benzene fused with cyclobutadiene, with the tropylium ion, and with the cyclopentadienyl anion were investigated. Subtraction of the isolated H2 isotropic value gave shielding increments (∆σ), which, when plotted against Cartesian coordinates of the probe over each hydrocarbon, gave representations of three- dimensional isotropic shielding increment surfaces. The results are related to the degree of bond length alternation, the extent of π electron delocalization, and (for the ions) the NPA charge d