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

[Image: see text] 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 (1)L(b), (1)L(a), and (1)B 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 (1)L(b) and (1)L(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 (1)L(b) bands of these cyclophanes were considerably large (∼10(–2)), whereas those for the (1)L(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.