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Control of the Diatropic π Ring Current in Strained Benzenes:  Effects of Annelation with Cyclopropa, Cyclobuta, and Cyclobutadieno Clamping Groups

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journal contribution
posted on 04.06.2002, 00:00 by Alessandro Soncini, Remco W. A. Havenith, Patrick W. Fowler, Leonardus W. Jenneskens, Erich Steiner
Direct visualization of the π current density maps of highly strained annelated benzenes containing cyclopropa, cyclobuta, and cyclobutadieno clamps, alone and in combination, using a reliable distributed-origin, coupled Hartree−Fock method, shows the robustness of the classical benzene diatropic π ring current. When only saturated clamps are used, the benzene ring current is essentially unchanged. In contrast, annelation with one or more cyclobutadieno clamps disrupts the benzene ring current. Analysis of orbital contributions to the current density maps gives a unified account of these observations in terms of the nature of the HOMO−LUMO transition.