Structurally
Well-Defined Sigmoidal Gold Clusters:
Probing the Correlation between Metal Atom Arrangement and Chiroptical
Response
Xin He
Yuechao Wang
Hong Jiang
Liang Zhao
10.1021/jacs.6b01658.s002
https://acs.figshare.com/articles/dataset/Structurally_Well_Defined_Sigmoidal_Gold_Clusters_Probing_the_Correlation_between_Metal_Atom_Arrangement_and_Chiroptical_Response/3189412
Asymmetric
arrangement of metal atoms is crucial for understanding
the chirality origin of chiral metal nanoclusters and facilitating
the design and development of new chiral catalysts and chiroptical
devices. Here, we describe the construction of four asymmetric gold
and gold–silver clusters by chirality transfer from diimido
ligands. The acquired metal clusters show strong circular dichroism
(CD) response with large anisotropy factors of up to 6 × 10<sup>–3</sup>, larger than the values of most reported chiral gold
nanoclusters. Regardless of the same absolute configuration of the
applied three diimido ligands, sigmoidal and reverse-sigmoidal arrangements
of gold atoms both can be achieved, which resultantly produce an opposite
Cotton effect within a specific absorption range. On the basis of
the detailed structural characterization via X-ray crystallography
and contrast experiments, the chirality contribution of the imido
ligand, the asymmetrically arranged metal cluster, and the chiral
arrangement of aromatic rings of phosphine ligands have been qualitatively
evaluated. Time-dependent DFT calculations reveal that the chiroptical
property of the acquired metal clusters is mainly influenced by the
asymmetrically arranged metal atoms. Correlation of asymmetric arrangements
of metal atoms in clusters with their chiroptical response provides
a viable means of fabricating a designable chiral surface of metal
nanoclusters and opens a broader prospect for chiral cluster application.
2016-04-12 00:00:00
diimido ligands
metal clusters show
chiral metal nanoclusters
metal atoms
designable chiral surface
Chiroptical Response Asymmetric arrangement
chiroptical
chiral gold nanoclusters
chirality
DFT
chiral cluster application
Metal Atom Arrangement