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Published on: April 14, 2020
Enantiomeric hexanuclear silver clusters: visible-near-infrared broadband emission and circularly polarized
Shi-Zhen Wang1, Jing-Kun Wang1, Ying Zeng1
1Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, School of Chemistry, IGCME, GBRCE for Functional Molecular Engineering, Sun Yat-Sen University, Guangzhou 510006, Guangdong, P. R. China. jiajh3@mail.sysu.edu.cn.
Abstract:
Chiral metal clusters with solid-state circularly polarized luminescence (CPL) properties remain largely underexplored. In particular, those capable of emitting across the visible to near-infrared (NIR) region-an essential feature for optoelectronic and interdisciplinary applications-are extremely rare. To advance such materials, a chiral transfer strategy was adopted to prepare a pair of enantiomeric silver clusters, denoted as R/S-Ag6, through the utilization of enantiopure chiral ligands (R-BTTH or S-BTTH). Single-crystal X-ray diffraction analyses reveal that, enabled by chirality induction, the R/S-Ag6 clusters along with Ag6 cores and Ag6S6 skeletons are mirror-symmetric. This can be attributed to the steric hindrance effect of chiral ligands. Comprehensive characterization studies were conducted using UV-Vis absorption spectroscopy, circular dichroism, DFT calculations, steady-state/transient fluorescence spectroscopy, and CPL spectroscopy. Notably, the R/S-Ag6 clusters exhibit broadband emission spanning 500-1200 nm and highly efficient CPL. This study endows the pair of enantiomeric metal clusters with extensive application prospects in the fields of chiral optoelectronics, nonlinear optics, and chiral catalysis.
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