Extreme Sensitivity of Circular Dichroism to Long-Range Excitonic Couplings in Helical Supramolecular Assemblies

Abstract

Circular dichroism (CD) spectroscopy is an ideal tool for studying the self-assembly of helical supramolecular assemblies since it is very sensitive to extended excitonic couplings between chiral chromophores. We show that the CD spectrum retains its high sensitivity to long-range interactions even in the presence of extreme disorder and strong interaction with vibrations when excitations are mainly localized on individual molecules. We derive a universal expression for the first moment of the CD spectrum of helical assemblies in terms of a modulated sum over excitonic couplings, which is independent of the strength of the energetic disorder, the spatial correlation of the disorder, and the strength of the interaction with vibrations. This demonstrates that excitonic couplings can be directly extracted from experimental CD spectra without having information about the energetic disorder and vibrational interactions. We apply our results to helical assemblies of functionalized chiral oligo(p-phenylenevinylene) molecules and show that existing theoretical values for the excitonic couplings should be adapted in order to obtain agreement with the experimental CD spectrum.