[ACIE] 我室郑南峰教授发表论文:From Symmetry Breaking to Unraveling Chirality of Metal Nanoclusters

我室郑南峰教授在 ACIE 上发表论文:From Symmetry Breaking to Unraveling Chirality of Metal Nanoclusters

文章链接:http://onlinelibrary.wiley.com/doi/10.1002/anie.201800327/full

摘要:

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.