Guest-Dependent Isomer Convergence of a Permanently Fluxional Coordination Cage

André P. Birvé, Harshal D. Patel, Jason R. Price, Witold M. Bloch, Thomas Fallon

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)
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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.

Original languageEnglish
Article numbere202115468
Number of pages5
JournalAngewandte Chemie - International Edition
Issue number9
Publication statusPublished - 21 Feb 2022
Externally publishedYes


  • Convergence
  • Coordination cage
  • Fluxional molecule
  • Host-guest chemistry
  • Self-assembly


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