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

DOI: 10.1021/jacs.8b09750 DOI Help

Authors: Weimin Xuan (The University of Glasgow) , Robert Pow (The University of Glasgow) , Nancy Watfa (The University of Glasgow) , Qi Zheng (The University of Glasgow) , Andrew J. Surman (The University of Glasgow) , De-Liang Long (The University of Glasgow) , Leroy Cronin (The University of Glasgow)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society

State: Published (Approved)
Published: November 2018
Diamond Proposal Number(s): 16085

Open Access Open Access

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 form 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 en-antiopure MBs. All the compounds share the same framework archetype, based on {Mo124Ce4}, which forms an intrinsically chiral or configurations controlled by the configurations of functionalized chiral amino acids. The chirality and stability of 1-5 in solution are confirmed by CD, 1H NMR and Electrospray Ion Mobility-Mass Spectrometry (ESI-IMS-MS) study. In addition, the framework of the {Mo124Ce4} MB not only behaves as host, able to trap a chiral {Mo8} cluster that is not accessible by traditional synthesis, but also exhibits an enzyme-like selective oxidation of tryptophan to kynurenine in-situ. This work demonstrates the potential and applicability of our synthetic strategy produce gigantic chiral POM clusters capable of host-guest chemistry and selective synthetic transformations.

Diamond Keywords: Peptides and proteins; Ligands; Monomers; Molecular structure; Cluster chemistry

Subject Areas: Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 03/12/2018 11:54


Discipline Tags:

Chemistry Inorganic Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)