Highly Elliptic Circular Dichroism of Copper Aspartate One-Dimensional Nanostructures across the Ultraviolet to Terahertz Ranges.

Choi, Won Jin; Kim, Ji-Young; Hwang, Myonghoo; Lim, Chung Man; Park, Bum Chul; Emre, Ahmet; Lee, Sang Hyun; Kotov, Nicholas A · Nano Lett · 2025

basic_science · Level V

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Abstract

Since the discovery of chirality, circular dichroism (CD) of mirror-asymmetric molecules has been studied across the ultraviolet, visible, and near-infrared ranges. Recently, chiroptical activity studies have expanded to the terahertz (THz) range, where resonance peaks originate from collective vibrations of tens and hundreds of atoms. In this study, we synthesized Cu<sup>2+</sup> coordination complexes with <i>L-</i> and <i>D-</i>aspartic acid as nanowires and nanorods and characterized their chiroptical activity across multiple frequency ranges. Both chiral nanostructures exhibit strong electronic CD (ECD), primarily from Cu<sup>2+</sup> <i>d</i>-<i>d</i> transitions, while vibrational CD (VCD) spectra show sharp C=O, C-H, and O-H vibronic peaks, indicating higher atomic defect densities in nanorods than nanowires. Although THz CD (TCD) spectra are broad, they exhibit ∼1000× greater ellipticity than ECD and VCD, perhaps warranting previous references to circular dichroism of nanostructures as giant. Comparative TCD analysis highlights strong chiral phonon sensitivity, underscoring its potential for probing defect densities and structural changes for various chiral nanostructures and (bio)crystals.