Electronic absorption and magnetic circular dichroism were recorded for five cyclophanes with ethano bridges: [2.2]paracyclophane, (1,2,4)[2.2.2]cyclophane, (1,2,4;1,2,5)[2.2.2]cyclophane, (1,2,3,4,5,6)(1,2,3,4,5,6)cyclophane, and trans-[2.2]metacyclophane. Spectral and structural analyses were based on geometry optimization and calculations of transition energies, carried out using density functional theory methods. The assignments have been proposed for several electronic transitions observed in the region below 52 000 cm−1. The observation of transitions which should be forbidden in the high D2h symmetry [2.2]paracyclophane suggests a twisted ground state structure of D2 symmetry, although the former structure with large amplitude vibrations at room temperature cannot be excluded. The PBE0 functional turned out to appropriately reproduce the inter-ring distances and electronic transition energies.
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See supplementary material at http://dx.doi.org/10.1063/1.3683454 for transition energies calculated using different functionals.
© 2012 American Institute of Physics.
2012
American Institute of Physics
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