Stereoselective assembly of gigantic chiral molybdenum blue wheels using lanthanide ions and amino acids

Xuan, W., Pow, R., Watfa, N., Zheng, Q., Surman, A. J. , Long, D.-L. and Cronin, L. (2019) Stereoselective assembly of gigantic chiral molybdenum blue wheels using lanthanide ions and amino acids. Journal of the American Chemical Society, 141(3), pp. 1242-1250. (doi:10.1021/jacs.8b09750) (PMID:30495944)

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Abstract

The synthesis of chiral polyoxometalates (POMs) is a challenge because of the difficulty to induce the formation of intrinsically chiral metal-oxo frameworks. Herein we report the stereoselective synthesis of a series of gigantic chiral Mo Blue (MB) POM clusters 1–5 that are formed by exploiting the synergy between coordinating lanthanides ions as symmetry breakers to produce MBs with chiral frameworks decorated with amino acids ligands; these promote the selective formation of enantiopure MBs. All the compounds share the same framework archetype, based on {Mo124Ce4}, which forms an intrinsically chiral Δ or Λ configurations, controlled by the configurations of functionalized chiral amino acids. The chirality and stability of 1–5 in solution are confirmed by circular dichroism, 1H NMR, and electrospray ion mobility–mass spectrometry studies. In addition, the framework of the {Mo124Ce4} MB not only behaves as a host able to trap a chiral {Mo8} cluster that is not accessible by traditional synthesis but also promotes the transformation of tryptophan to kynurenine in situ. This work demonstrates the potential and applicability of our synthetic strategy to produce gigantic chiral POM clusters capable of host–guest chemistry and selective synthetic transformations.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Xuan, Mr Weimin and Watfa, Dr Nancy and Pow, Mr Robert William and Zheng, Ms Qi and Long, Dr Deliang and Cronin, Professor Lee and Surman, Dr Andrew
Authors: Xuan, W., Pow, R., Watfa, N., Zheng, Q., Surman, A. J., Long, D.-L., and Cronin, L.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of the American Chemical Society
Publisher:American Chemical Society
ISSN:0002-7863
ISSN (Online):1520-5126
Published Online:29 November 2018
Copyright Holders:Copyright © 2018 American Chemical Society
First Published:First published in Journal of the American Chemical Society 141(3): 1242-1250
Publisher Policy:Reproduced under a Creative Commons License

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
577391Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/J015156/1CHEM - CHEMISTRY
646611Programmable 'Digital' Synthesis for Discovery and Scale-up of Molecules, Clusters and NanomaterialsLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/L023652/1CHEM - CHEMISTRY
562821Innovative Manufacturing Research Centre for Continuous Manufacturing and Crystallisation (CMAC)Leroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/I033459/1CHEM - CHEMISTRY
577391Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/J015156/1CHEM - CHEMISTRY
616021Energy and the Physical Sciences: Hydrogen Production using a Proton Electron BufferLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/K023004/1CHEM - CHEMISTRY
599451Microscale Chemically Reactive Electronic AgentsLeroy CroninEuropean Commission (EC)FP7 ICT MICRE318671CHEM - CHEMISTRY
685741SMARTPOM: Artificial-Intelligence Driven Discovery and Synthesis of Polyoxometalate ClustersLeroy CroninEuropean Research Council (ERC)670467CHEM - CHEMISTRY

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