This paper reviews the recent advances in experiment and theory of the induction of chiroptical effects, primarily circular dichroism (CD), at the plasmonic and excitonic resonances of achiral inorganic nanocrystals (NCs) capped and/or formed with chiral molecules. It also addresses stronger chiroptical effects obtained in intrinsically chiral inorganic nanostructures obtained from growing enantiomeric excess of intrinsically chiral NCs or arranging achiral plasmonic particles in chiral configurations. The accumulated experimental data and theory on various CD induction mechanisms provide an extended set of tools to properly analyze and understand the electromagnetic influence of chiral molecules on inorganic particles and obtain new general insights into the interaction of capping molecules with inorganic NCs. Among the field-induced CD mechanisms developed recently one can name the Coulomb (near-field, dipolar) mechanism for nanostructures much smaller than the wavelength, and for larger nanostructures, the electromagnetic (effective chiral medium), and intrinsically chiral plasmonic mechanisms.
Circular dichroism (CD) induced at exciton transitions by chiral ligands attached to single component and core/shell colloidal quantum dots (QDs) was used to study the interactions between QDs and their capping ligands. Analysis of the CD line shapes of CdSe and CdS QDs capped with l-cysteine reveals that all of the features in the complex spectra can be assigned to the different excitonic transitions. It is shown that each transition is accompanied by a derivative line shape in the CD response, indicating that the chiral ligand can split the exciton level into two new sublevels, with opposite angular momentum, even in the absence of an external magnetic field. The role of electrons and holes in this effect could be separated by experiments on various types of core/shell QDs, and it was concluded that the induced CD is likely related to interactions of the highest occupied molecular orbitals of the ligands with the holes. Hence, CD was useful for the analysis of hole level–ligand interactions in quantum semiconductor heterostructures, with promising outlook toward better general understanding the properties of the surface of such systems.
11 December 2012 in Angewandte Chemie International Edition