Circular Dichroisms of Mono- and Dibromo[2.2]paracyclophanes: A Combined Experimental and Theoretical Study

Circular dichroisms (CDs) of planar chiral 4-bromo[2.2]­paracyclophane (1) and three isomeric dibromo[2.2]­paracyclophanes (p-2, m′-2, and o′-2) were investigated experimentally and theoretically. They all exhibited strong multisignate Cotton effects (CEs) at the ¹L_b, ¹L_a, and ¹B transitions of the component (bromo)­benzene chromophore and were comparable to each other. For all of the cyclophanes examined, the enantiomer that eluted earlier from a chiral high-performance liquid chromatography column (Chiralcel IA or IB) exhibited negative and positive CEs at the ¹L_b and ¹L_a bands, respectively, which were followed by a more complicated pattern of CDs at the higher-energy bands. These CD features were well reproduced by quantum chemical calculations, allowing us to unambiguously assign the absolute configurations of the first-eluted enantiomers as R_p in all of the cases examined. Interestingly, the CDs of 1 and 2, although largely comparable in shape, were still sensitive to the number and pattern of bromine substitution, showing closer resemblance between m′-2 and o′-2 and between p-2 and 1. The theoretical calculations also reproduced successfully these spectral resemblance between them. The anisotropy (g) factors for the ¹L_b bands of these cyclophanes were considerably large (∼10^–2), whereas those for the ¹L_a band were conventional in the order of 10^–3. In addition, a weak CE was observed in the low-energy region at around 320 nm, which turned out to originate from the interplanar interaction and is hence assigned to the “cyclophane band”. The experimental g factors of this band were fairly large in the order of 10^–2, but the computation turned out to be quite challenging and were less well reproduced theoretically, ascribable to the forbidden nature of the transition.