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Chiral semiconductor nanocrystals, or quantum dots (QDs), are promising materials for applications in biological sensing, photonics, and spin-polarized devices. Many of these applications rely on large dissymmetry, or g-factors, the difference in absorbance between left- and right-handed circularly polarized light compared to the unpolarized absorbance. The majority of chiral QDs, specifically CdSe, reported to date have used thiolated amino acid ligands to introduce chirality onto the nanoparticles, but these systems have ultimately reported small g-factors of ∼2 × 10-4. In an effort to realize chiral CdSe QDs with higher g-factors and to expand the set of designer chiral semiconductor nanocrystals, we have employed chiral carboxylic acids as a distinct class of ligands for chiral CdSe nanoparticles. Through this family of chiral carboxylic acid ligands, we performed a direct comparison between carboxylate-bound and thiolate-bound chiral CdSe QDs. Spectral analysis revealed that the resulting circular dichroism shifts originate from the splitting of the exciton by the ligand-nanocrystal interaction. Subsequent examination of a series of chiral carboxylic acid ligands revealed a 30-fold range in g-factor through relatively small changes in the structure of the ligand. Finally, we showed that increasing the number of stereocenters on the ligand can further enhance the dissymmetry factors. This versatile and tunable combination of nanocrystals and ligands will inform future designs of chiral nanomaterials and their applications.
Bibliographical noteFunding Information:
This work was supported by the Air Force Office of Scientific Research under Contract Number FA9550-16-1-0282. Circular dichroism experiments reported in this paper were performed at the Biophysical Technology Center, University of Minnesota Department of Biochemistry, Molecular Biology, and Biophysics. Transmission electron microscopy and infrared spectroscopy experiments were carried out in the Characterization Facility, University of Minnesota, which receives partial support from NSF through the MRSEC program. The authors would like to thank Whitney Wenger for assistance with DLS measurements and analysis, as well as Pavlos Pachidis and Professor Mahesh Mahanthappa for valuable discussions.
© 2017 American Chemical Society.
- carboxylic acid
- chiral semiconductor nanocrystals
- circular dichroism
- ligand-induced optical activity
- quantum dots
How much support was provided by MRSEC?
Reporting period for MRSEC
- Period 4
PubMed: MeSH publication types
- Journal Article
- Research Support, U.S. Gov't, Non-P.H.S.