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 дек 2022
Accepted
01 фев 2023
First published
01 фев 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

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements