Structure and NMR spectra of cyclophanes with unsaturated bridges (cyclophenes)

Abstract

The calculated structures of several known and hypothetical cyclophanes with ethylene bridges (cyclophenes) are reported together with experimental and calculated values of their NMR parameters. Of the exchange-correlation functionals and basis sets used in this work, only the ωB97X-D/6-311++G(2d,2p) and ωB97X-D/cc-pVQZ yielded values of the C(sp3)-C(sp3) bond length close to the experimental data, although significant differences still remain. As far as the NMR parameters are concerned, except for close-lying signals, chemical shifts and coupling constants calculated at the ωB97X-D/cc-pVQZ level reproduce in most cases the experimental trends. Contrary to the calculations of geometries, an agreement between the values of the NMR parameters obtained at ωB97X-D/cc-pVQZ level and the experimental ones is the poorest compared with that of the ωB97X-D/6-311++G(2d,2p) one. Taking into account that the results of the different calculations show the same qualitative trends in most cases, we believe that they correctly describe the structure and properties of the hypothetical molecules studied here.