Restriction of intramolecular rotation for functionalizing metal nanoclusters
Junsheng Xin1,2, Jing Xu1, Chen Zhu1
1Department of Chemistry, Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui University Hefei Anhui 230601 China zhangqiong.314@163.com kangxi_chem@ahu.edu.cn zmz@ahu.edu.cn.
Abstract:
The restriction of intramolecular rotation has been extensively exploited to trigger the property enhancement of nanocluster-based materials. However, such a restriction is induced mainly by intermolecular aggregation. The direct restriction of intramolecular rotation of metal nanoclusters, which could boost their properties at the single molecular level, remains rarely explored. Here, ligand engineering was applied to activate intramolecular interactions at the interface between peripheral ligands and metallic kernels of metal nanoclusters. For the newly reported Au4Ag13(SPhCl2)9(DPPM)3 nanocluster, the molecule-level interactions between the Cl terminals on thiol ligands and the Ag atoms on the cluster kernel remarkably restricted the intramolecular rotation, endowing this robust nanocluster with superior thermal stability, emission intensity, and non-linear optical properties over its cluster analogue. This work presents a novel case of the restriction of intramolecular rotation (i.e., intramolecular interaction-induced property enhancement) for functionalizing metal clusters at the single molecular level.
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