Oral Presentation The 35th Biennial Conference of the Society of Crystallographers in Australia and New Zealand 2024 (Crystal 35)

Halide-triggered assembly and selective bisulfate recognition in a quadruply interlocked coordination cage  (109447)

Jemma Virtue 1 , Steven Tsoukatos 1 , Martin Johnston 1 , Witold Bloch 1
  1. College of Science and Engineering, Flinders University, Adelaide, South Australia, Australia

Interlocked coordination cages are a class of multi-cavity architectures with applications in selective anion recognition, adaptive sensing and catalysis. Their synthesis has attracted considerable attention with unique characteristics including partitioned cavities and mechanical properties. Allosteric guest recognition,stimuli-responsive motion2-4 and photocatalytic activity5-7 have all been exhibited within these systems – properties not observed within their isolated monomeric units. By controlling the partitioning of their cavities through anion templates selective molecular recognition may be accessed, yet this still remains as a challenge. We showed that a thermodynamically stable [Pd2L4](BF4)4 monomeric cage assembled from a bis-monodentate ligand featuring a semi-flexible, non-coordinating bis-pyrazole backbone could be isolated through appropriate solvent choice and stoichiometric control. As a result of its idealised dimensions with respect to the counter-ion volume, NMR, ESI-MS, and X-ray analyses revealed that halides trigger the interpenetration of this cage into a [X@Pd4L8]7+ dimer (X = Cl or Br) in which the halides reside only in the central pocket. Comparing the host-guest chemistry between the Br and Cl templated dimers on a suite of anions revealed large differences in binding strength (up to an order of magnitude in favour of the Cltemplate), despite their subtle structural differences. Furthermore, we found this type of interlocked host facilitates exceptional binding recognition for the bisulfate anion in the two outer pockets (up to 106 M-1 in MeCN), strongly outcompeting other tetrahedral anions of a similar size. 

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