title: Spatial structure and NMR spectra of strained [2.2.2]cyclophanes.
abstract: The chemical shifts and coupling constants in the NMR spectra of the title compounds are influenced by their strain and the proximity of the aromatic rings. These parameters are studied by density functional theory (DFT) calculations for 1-4 and measured for 3 and 4. We find that, in spite of the strain, the calculations reproduce the experimental values satisfactorily. This finding is of special importance for novel hypothetical molecules like hexahydrosuperphane 5 for their future identification and in searches of hydrocarbons exhibiting unusual NMR parameters. Our results demonstrate the influence of strain on the parameters studied. Most proton and carbon chemical shifts for the molecules under study having nonplanar aromatic rings differ considerably from the corresponding values for the relatively unstrained trimethylbenzenes and ethylbenzene. In addition, the calculated values of the coupling constants through three bonds in most cases do not follow Karplus relation.
authors.affiliation: Institute of Physical Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Kasprzaka 44/52, Poland. dodziuk@ichf.edu.pl
authors.forename: Helena
authors.initials: H
authors.lastname: Dodziuk
authors.forename: Maciej
authors.initials: M
authors.lastname: Ostrowski
authors.forename: Kenneth
authors.initials: K
authors.lastname: Ruud
authors.forename: Jarosław
authors.initials: J
authors.lastname: Jaźwiński
authors.forename: Henning
authors.initials: H
authors.lastname: Hopf
authors.forename: Wiktor
authors.initials: W
authors.lastname: Koźmiński