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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This content will become publicly available on June 18, 2024
Can we still measure circular dichroism with circular dichroism spectrometers: The dangers of anisotropic artifacts
Chiral materials with strong linear anisotropies are difficult to accurately characterize with circular dichroism (CD) because of artifactual contributions to their spectra from linear dichroism (LD) and birefringence (LB). Historically, researchers have used a second‐order Taylor series expansion on the Mueller matrix to model the LDLB interaction effects on the spectra in conventional materials, but this approach may no longer be sufficient to account for the artifactual CD signals in emergent materials. In this work, we present an expression to model the measured CD using a third‐order expansion, which introduces “pairwise interference” terms that, unlike the LDLB terms, cannot be averaged out of the signal. We find that the third‐order pairwise interference terms can make noticeable contributions to the simulated CD spectra. Using numerical simulations of the measured CD across a broad range of linear and chiral anisotropy parameters, the LDLB interactions are most prominent in samples that have strong linear anisotropies (LD, LB) but negligible chiral anisotropies, where the measured CD strays from the chirality‐induced CD by factors greater than 103. Additionally, the pairwise interactions are most significant in systems with moderate‐to‐strong chiral and linear anisotropies, where the measured CD is inflated twofold, a figure that grows as linear anisotropies approach their maximum. In summary, media with moderate‐to‐strong linear anisotropy are in great danger of having their CD altered by these effects in subtle manners. This work highlights the significance of considering distortions in CD measurements through higher‐order pairwise interference effects in highly anisotropic nanomaterials.
more » « less- Award ID(s):
- 2003431
- NSF-PAR ID:
- 10441929
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Chirality
- Volume:
- 35
- Issue:
- 11
- ISSN:
- 0899-0042
- Format(s):
- Medium: X Size: p. 846-855
- Size(s):
- ["p. 846-855"]
- Sponsoring Org:
- National Science Foundation
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