From Symmetry Breaking to Unraveling the Origin of the Chirality of Ligated Au13 Cu2 Nanoclusters.
Guocheng DengSami MalolaJuanzhu YanYingzi HanPeng YuanChaowei ZhaoXiting YuanShuichao LinZichao TangBoon K TeoHannu HäkkinenNan-Feng ZhengPublished in: Angewandte Chemie (International ed. in English) (2018)
A general method, using mixed ligands (here diphosphines and thiolates) is devised to turn an achiral metal cluster, Au13 Cu2 , into an enantiomeric pair by breaking (lowering) the overall molecular symmetry with the ligands. Using an achiral diphosphine, a racemic [Au13 Cu2 (DPPP)3 (SPy)6 ]+ was prepared which crystallizes in centrosymmetric space groups. Using chiral diphosphines, enantioselective synthesis of an optically pure, enantiomeric pair of [Au13 Cu2 ((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.
Keyphrases
- sensitive detection
- capillary electrophoresis
- density functional theory
- quantum dots
- aqueous solution
- reduced graphene oxide
- metal organic framework
- mass spectrometry
- fluorescent probe
- deep learning
- visible light
- optical coherence tomography
- photodynamic therapy
- gold nanoparticles
- molecular dynamics simulations
- convolutional neural network
- ionic liquid
- big data
- molecular docking
- nk cells
- artificial intelligence