From Symmetry Breaking to Unraveling the Origin of the Chirality of Ligated Au13Cu2 Nanoclusters
Deng, G., Malola, S., Yan, J., Han, Y.-Z., Yuan, P., Zhao, C., . . . Zheng, N. (2018). From Symmetry Breaking to Unraveling the Origin of the Chirality of Ligated Au13Cu2 Nanoclusters. Angewandte Chemie International Edition, 57 (13), 3421-3425. doi:10.1002/anie.201800327
Published inAngewandte Chemie International Edition
© 2018 Wiley‐VCH Verlag GmbH & Co. This is a final draft version of an article whose final and definitive form has been published by Wiley‐VCH Verlag GmbH & Co. Published in this repository with the kind permission of the publisher.
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 in the range of 250–500 nm with maximum anisotropy factors of 1.2×10−3. 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.
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