郑州大学藏双全团队报道了同构对映体Ag12Ag32和Au12Ag32团簇的非手性-核-金属变化引发圆偏正磷光。相关研究成果发表在2022年10月24日出版的国际学术期刊《美国化学会杂志》。

理解手性纳米结构中的手性或非手性部分如何在原子水平上促进圆偏振光发射（CPLE）是至关重要的。

该文中，研究人员报道了两对原子精确的对映体：均银（R/S-Ag12Ag32）和杂金属（R/S-S-Au12Ag32）簇。R/S-Ag12Ag32的几何手性来自于由Ag32（R/S-PS）24的正集团组成的手性配体和界面。S2–@M12@S8的无侧核部分中从Ag12到Au12的完全金属变化，产生激活CPLE的同晶异金属R/S-Au12Ag32。

研究人员进一步量化了非手性部分和手性部分的贡献，并首次揭示了键合处的杂金属键合（Au12-Ag32）改变了轨道的离域，以及非手性和手性部分在涉及电子跃迁的轨道中的比例，从而激活了CPLE。基于这些独特的原子精确的同手性金属簇，该工作为手性金属簇的手性反应的起源提供了新的视角，为推动CPLE纳米颗粒的发展铺平了道路。

附：英文原文

Title: Achiral-Core-Metal Change in Isomorphic Enantiomeric Ag12Ag32 and Au12Ag32 Clusters Triggers Circularly Polarized Phosphorescence

Author: Yu-Jin Kong, Jia-Hua Hu, Xi-Yan Dong, Yubing Si, Zhao-Yang Wang, Xi-Ming Luo, Hong-Ren Li, Zongwei Chen, Shuang-Quan Zang, Thomas C. W. Mak

Issue&Volume: October 24, 2022

Abstract: Understanding how the chiral or achiral section in chiral nanostructures contributes to circularly polarized light emission (CPLE) at the atomic level is of fundamental importance. Here, we report two pairs of atomically precise enantiomers of homosilver (R/S-Ag12Ag32) and heterometal (R/S-Au12Ag32) clusters. The geometrical chirality of R/S-Ag12Ag32 arises from the chiral ligand and interface consisting of positive moieties of Ag32(R/S-PS)24. The circular dichroism of R/S-Ag12Ag32 is active, but CPLE-silent. A complete metal change from Ag12 to Au12 in the achiral core section of S2–@M12@S8 engenders isomorphous heterometal R/S-Au12Ag32, which activates CPLE. We further quantify the contributions of achiral and chiral sections and for the first time unveil that heterometal bonding (Au12-Ag32) at the linkage varies the delocalization of orbitals and proportion of achiral and chiral section in electron transition-involved orbitals, thus activating CPLE. Based on these unique atomically precise homochiral metal clusters, our work provides a new insight into the contributions of achiral and chiral sections to the origin of chiroptical response of chiral metal clusters, paving the way to advance the development of CPLE nanoparticles.

DOI: 10.1021/jacs.2c05881

Source: https://pubs.acs.org/doi/10.1021/jacs.2c05881