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[ACIE] Prof.Nanfeng Zheng published a paper entitled "From Symmetry Breaking to Unraveling Chirality of Metal Nanoclusters"


Title: From Symmetry Breaking to Unraveling Chirality of Metal Nanoclusters

Authors: Guocheng Deng,Sami Malola,Juanzhu Yan,Ying-Zi Han,Peng Yuan,Chaowei Zhao,Xiting Yuan,Shuichao Lin,Zichao Tang,Boon K. Teo,Hannu Häkkinen,Nanfeng Zheng


A general method, using mixed ligands (here diphosphines and thiolates) is devised to turn an achiral metal cluster, Au13Cu2, into an enantiomeric pair by breaking (lowering) the overall molecular symmetry with the ligands. Using an achiral diphosphine, a racemic [Au13Cu2(DPPP)3(SPy)6]+ was prepared which crystallizes in centrosymmetric space groups. Using chiral diphosphines, enantioselective synthesis of an optically pure, enantiomeric pair of [Au13Cu2((2r,4r)/(2s,4s)-BDPP)3(SPy)6]+ was achieved in one pot. Their circular dichroism (CD) spectra give perfect mirror images from 250-500nm with maximum anisotropy factors of 1.2 × 10-3. Density Functional Theory (DFT) calculations provided good correlations with the observed CD spectra of the enantiomers and, more importantly, revealed the origin of the chirality. Racemization studies show high stability (no racemization at 70°C) of these chiral nanoclusters, which hold great promise in applications such as asymmetry catalysis.