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Type: Journal article
Title: Guest-dependent isomer convergence of a permanently fluxional coordination cage
Author: Birve, A.
Patel, H.D.
Price, J.R.
Bloch, W.M.
Fallon, T.
Citation: Angewandte Chemie International Edition, 2022; 61(9):e202115468-1-e202115468-6
Publisher: Wiley
Issue Date: 2022
ISSN: 1433-7851
Statement of
André P. Birvé, Harshal D. Patel, Jason R. Price, Witold M. Bloch, Thomas Fallon
Abstract: A fluxional bis-monodentate ligand, based on the archetypal shape-shifting molecule bullvalene, self-assembles with M2+ (M = Pd2+ or Pt2+) to produce a highly complex ensemble of permanently fluxional coordination cages. Metal-mediated self-assembly selects for an M2L4 architecture while maintaining shape-shifting ligand complexity. A second level of simplification is achieved with guest-exchange; the binding of halides within the M2L4 cage mixture results in a convergence to a cage species with all four ligands present as the "B isomer". Within this confine, the reaction graph of the bullvalene is greatly restricted, but gives rise to a mixture of 38 possible diastereoisomers in rapid exchange. X-ray crystallography reveals a preference for an achiral form consisting of both ligand enantiomers. Through a combination of NMR spectroscopy and DFT calculations, we elucidate the restricted isomerisation pathway of the permanently fluxional M2L4 assembly.
Keywords: convergence * coordination cage * fluxional molecule * host-guest chemistry * self-assembly
Description: First published: 01 December 2021
Rights: © 2021The Authors.Angewandte Chemie International Edition published by Wiley-VCHGmbH.This is an open access article under the terms of the Creative Commons Attribution Non-Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes
DOI: 10.1002/anie.202115468
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Appears in Collections:Chemistry publications

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