Issue 8, 2023

IrAu12 superatom modified by chiral diphosphines: doping-induced enhancement of chiroptical activity

Abstract

Gold superatoms modified by chiral ligands are a new class of chiroptical nanomaterials, but improvement of their chiroptical properties, such as circular dichroism (CD) and circularly polarized luminescence (CPL), remains a challenge. In this work, we studied the effects of single-atom doping on the chiroptical properties of a representative Au13 superatom using [Au13((R,R)-DIPAMP)5Cl2]3+ and [Au13((S,S)-DIPAMP)5Cl2]3+ (Au13-R/S; DIPAMP = 1,2-bis[(2-methoxyphenyl)phenylphosphino]ethane). We synthesized an enantiomeric pair of superatoms: [IrAu12((R,R)-DIPAMP)5Cl2]+ and [IrAu12((S,S)-DIPAMP)5Cl2]+ (IrAu12-R/S). Single-crystal X-ray diffraction analysis revealed that the icosahedral Ir@Au12 core of IrAu12-R/S was more twisted along the Cl–Au–Ir–Au–Cl axis compared with the Au13 core of Au13-R/S, leading to a larger absorption anisotropy factor. IrAu12-R/S exhibited a much higher photoluminescence quantum yield (∼70%) compared with Au13-R/S (15%) due to a larger energy gap between the highest occupied and the lowest unoccupied molecular orbitals. Although Ir doping did not appreciably enhance the photoluminescence anisotropy factors, the brightness of the CPL of IrAu12-R/S was five times higher than that of Au13-R/S. This work provides a rational guide for improving the chiroptical activity of Au superatoms via the doping-mediated manipulation of the geometric and electronic structures.

Graphical abstract: IrAu12 superatom modified by chiral diphosphines: doping-induced enhancement of chiroptical activity

Supplementary files

Article information

Article type
Paper
Submitted
14 Dec. 2022
Accepted
01 Febr. 2023
First published
01 Febr. 2023
This article is Open Access
Creative Commons BY-NC license

J. Mater. Chem. C, 2023,11, 3095-3100

IrAu12 superatom modified by chiral diphosphines: doping-induced enhancement of chiroptical activity

H. Hirai, T. Nakashima, S. Takano, Y. Shichibu, K. Konishi, T. Kawai and T. Tsukuda, J. Mater. Chem. C, 2023, 11, 3095 DOI: 10.1039/D2TC05321G

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