TY - JOUR
T1 - Dynamic Tuning of the Bandgap of CdSe Quantum Dots through Redox-Active Exciton-Delocalizing N-Heterocyclic Carbene Ligands
AU - Westmoreland, Dana E.
AU - López-Arteaga, Rafael
AU - Kantt, Leanna Page
AU - Wasielewski, Michael R.
AU - Weiss, Emily A.
N1 - Funding Information:
This work was primarily funded by the Air Force Office of Scientific Research (AFOSR, grant number FA9550-20-1-0364). The authors also received support from the National Institutes of Health (grant no. R21GM127919) and the National Science Foundation under Award CHE-1925690 (M.R.W.). We utilized instrumentation in the IMSERC facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF ECCS-1542205), the NIH (1S10OD012016-01/1S10RR019071-01A1), the state of Illinois, and the International Institute for Nanotechnology (IIN). This work made use of the EPIC facilities of Northwestern University’s NU ANCE Center. We thank Dr. Mark Maskeri for providing materials for preliminary experiments and David D. Xu for assistance with STEM image collection.
Publisher Copyright:
© 2022 American Chemical Society.
PY - 2022/3/16
Y1 - 2022/3/16
N2 - Ligands that enable the delocalization of excitons beyond the physical boundary of the inorganic core of semiconductor quantum dots (QDs), called "exciton-delocalizing ligands (EDLs)", offer the opportunity to design QD-based environmental sensors with dynamically responsive optical spectra, because the degree of exciton delocalization depends on the electronic structure of the EDL. This paper demonstrates dynamic, reversible tuning of the optical bandgap of a dispersion of CdSe QDs through the redox states of their 1,3-dimesitylnaphthoquinimidazolylidene N-heterocyclic carbene (nqNHC) ligands. Upon binding of the nqNHC ligands to the QD, the optical bandgap bathochromically shifts by up to 102 meV. Electrochemical reduction of the QD-bound nqNHC ligands shifts the bandgap further by up to 25 meV, a shift that is reversible upon reoxidation.
AB - Ligands that enable the delocalization of excitons beyond the physical boundary of the inorganic core of semiconductor quantum dots (QDs), called "exciton-delocalizing ligands (EDLs)", offer the opportunity to design QD-based environmental sensors with dynamically responsive optical spectra, because the degree of exciton delocalization depends on the electronic structure of the EDL. This paper demonstrates dynamic, reversible tuning of the optical bandgap of a dispersion of CdSe QDs through the redox states of their 1,3-dimesitylnaphthoquinimidazolylidene N-heterocyclic carbene (nqNHC) ligands. Upon binding of the nqNHC ligands to the QD, the optical bandgap bathochromically shifts by up to 102 meV. Electrochemical reduction of the QD-bound nqNHC ligands shifts the bandgap further by up to 25 meV, a shift that is reversible upon reoxidation.
UR - http://www.scopus.com/inward/record.url?scp=85126295874&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85126295874&partnerID=8YFLogxK
U2 - 10.1021/jacs.1c12842
DO - 10.1021/jacs.1c12842
M3 - Article
C2 - 35254065
AN - SCOPUS:85126295874
VL - 144
SP - 4300
EP - 4304
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 10
ER -