Dynamic Tuning of the Bandgap of CdSe Quantum Dots through Redox-Active Exciton-Delocalizing N-Heterocyclic Carbene Ligands.

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.

Light-Triggered Switching of Quantum Dot Photoluminescence through Excited-State Electron Transfer to Surface-Bound Photochromic Molecules.

This paper describes reversible "on-off" switching of the photoluminescence (PL) intensity of CdSe quantum dots (QDs), mediated by photochromic furylfulgide carboxylate (FFC) molecules chemisorbed to the surfaces of the QDs. Repeated cycles of UV and visible illumination switch the FFC between "closed" and "open" isomers. Reversible switching of the QDs' PL intensity by >80% is enabled by different rates and yields of PL-quenching photoinduced electron transfer (PET) from the QDs to the respective isomers. This difference is consistent with cyclic voltammetry measurements and density functional calculations of the isomers' frontier orbital energies. This work demonstrates fatigue-resistant modulation of the PL of a QD-molecule complex through remote control of PET. Such control potentially enables applications, such as all-optical memory, sensing, and imaging, that benefit from a fast, tunable, and reversible response to light stimuli.

N-Heterocyclic Carbenes as Reversible Exciton-Delocalizing Ligands for Photoluminescent Quantum Dots.

Delocalization of excitons within semiconductor quantum dots (QDs) into states at the interface of the inorganic core and organic ligand shell by so-called "exciton-delocalizing ligands (EDLs)" is a promising strategy to enhance coupling of QD excitons with proximate molecules, ions, or other QDs. EDLs thereby enable enhanced rates of charge carrier extraction from, and transport among, QDs and dynamic colorimetric sensing. The application of reported EDLs-which bind to the QDs through thiolates or dithiocarbamates-is however limited by the irreversibility of their binding and their low oxidation potentials, which lead to a high yield of photoluminescence-quenching hole trapping on the EDL. This article describes a new class of EDLs for QDs, 1,3-dimethyl-4,5-disubstituted imidazolylidene N-heterocyclic carbenes (NHCs), where the 4,5-substituents are Me, H, or Cl. Postsynthetic ligand exchange of native oleate capping ligands for NHCs results in a bathochromic shift of the optical band gap of CdSe QDs (R = 1.17 nm) of up to 111 meV while the colloidal stability of the QDs is maintained. This shift is reversible for the MeNHC-capped and HNHC-capped QDs upon protonation of the NHC. The magnitude of exciton delocalization induced by the NHC (after scaling for surface coverage) increases with the increasing acidity of its π system, which depends on the substituent in the 4,5-positions of the imidazolylidene. The NHC-capped QDs maintain photoluminescence quantum yields of up to 4.2 ± 1.8% for shifts of the optical band gap as large as 106 meV.

Properties of quantum dots coupled to plasmons and optical cavities.

Quantum electrodynamics is rapidly finding a set of new applications in thresholdless lasing, photochemistry, and quantum entanglement due to the development of sophisticated patterning techniques to couple nanoscale photonic emitters with photonic and plasmonic cavities. Colloidal and epitaxial semiconductor nanocrystals or quantum dots (QDs) are promising candidates for emitters within these architectures but are dramatically less explored in this role than are molecular emitters. This perspective reviews the basic physics of emitter-cavity coupling in the weak-to-strong coupling regimes, describes common architectures for these systems, and lists possible applications (in particular, photochemistry), with a focus on the advantages and issues associated with using QDs as the emitters.

pH-Dependent structure of water-exposed surfaces of CdSe quantum dots.

Increasing negative charge density at the surfaces of CdSe quantum dots (QDs) effects a bathochromic shift of their ground state optical spectra with increasing pH due to electrostatic and chemical modifications at the QD surface. These modifications are enabled by weakly-bound ligands that expose the surface to the aqueous environment.

Organic-to-Aqueous Phase Transfer of Cadmium Chalcogenide Quantum Dots using a Sulfur-Free Ligand for Enhanced Photoluminescence and Oxidative Stability.

This paper describes a procedure for transferring colloidal CdS and CdSe quantum dots (QDs) from organic solvents to water by exchanging their native hydrophobic ligands for phosphonopropionic acid (PPA) ligands, which bind to the QD surface through the phosphonate group. This method, which uses dimethylformamide as an intermediate transfer solvent, was developed in order to produce high-quality water soluble QDs with neither a sulfur-containing ligand nor a polymer encapsulation layer, both of which have disadvantages in applications of QDs to photocatalysis and biological imaging. CdS (CdSe) QDs were transferred to water with a 43% (48%) yield using PPA. The photoluminescence (PL) quantum yield for PPA-capped CdSe QDs is larger than that for QDs capped with the analogous sulfur-containing ligand, mercaptopropionic acid (MPA), by a factor of four at pH 7, and by up to a factor of 100 under basic conditions. The MPA ligands within MPA-capped QDs oxidize at Eox ~ +1.7 V vs. SCE, whereas cyclic voltammograms of PPA-capped QDs show no discerible oxidation peaks at applied potentials up to +2.5 V vs. SCE. The PPA-capped QDs are chemically and colloidally stable for at least five days in the dark, even in the presence of O2, and are stable when continuously illuminated for five days, when oxygen is excluded and a sacrificial reductant is present to capture photogenerated holes.