Post-synthetic phase transfer ligand exchange has been established as a simple, reliable, and versatile method for the synthesis of chiral, optically active colloidal nanocrystals displaying circular dichroism (CD) and circularly polarized luminescence (CPL). Herein we present a water-free and purification-free cyclohexane → methanol ligand exchange system that led to the synthesis of stable, non-aggregating chiral and fluorescent cadmium sulfide quantum dots (CdS QDs). Absorption and emission studies revealed that the carboxylate capping ligands can tune the band gap by up to 65 meV as well as control the band gap and deep trap emission pathways. The CD data revealed that the addition of a 2nd stereogenic center did not automatically lead to an increase of the CD anisotropy of QDs, but rather match/mismatch cooperativity effects must be considered in the transfer of the chirality from the capping ligands to the achiral nanocrystals. Variation in position of the functional groups as well as the chemical identity of the functional groups impacted both the shape and anisotropy of the induced CD spectra and revealed the importance of the functional groups’ coordination and polarity on the binding geometry and induced chiroptical properties. Finally, we describe the first example where CD spectra of QDs capped with the same ligand and dissolved in the same solvent displayed very different spectral profiles. This work provides deeper insight into induced CD of QDs and paves the path to rational design of chiral nanomaterials.
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Polysalt ligands achieve higher quantum yield and improved colloidal stability for CsPbBr 3 quantum dots
Colloidal lead halide perovskite quantum dots (PQDs) are relatively new semiconductor nanocrystals with great potential for use in optoelectronic applications. They also present a set of new scientifically challenging fundamental problems to investigate and understand. One of them is to address the rather poor colloidal and structural stability of these materials under solution phase processing and/or transfer between solvents. In this contribution, we detail the synthesis of a new family of multi-coordinating, bromide-based polysalt ligands and test their ability to stabilize CsPbBr 3 nanocrystals in polar solutions. The ligands present multiple salt groups involving quaternary cations, namely ammonium and imidazolium as anchors for coordination onto PQD surfaces, along with several alkyl chains with varying chain length to promote solubilization in various conditions. The ligands provide a few key benefits including the ability to repair damaged surface sites, allow rapid ligand exchange and phase transfer, and preserve the crystalline structure and morphology of the nanocrystals. The polysalt-coated PQDs exhibit near unity PLQY and significantly enhanced colloidal stability in ethanol and methanol.
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- NSF-PAR ID:
- 10327885
- Date Published:
- Journal Name:
- Nanoscale
- Volume:
- 13
- Issue:
- 39
- ISSN:
- 2040-3364
- Page Range / eLocation ID:
- 16705 to 16718
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d1nr04753a
