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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
Published on: March 24, 2018
Towards a Stronger Halogen Bond Involving Astatine: Unexpected Adduct with Bu3 PO Stabilized by Hydrogen Bonding
Lu Liu1, Ning Guo1, Julie Champion1
1SUBATECH, UMR CNRS 6457, IN2P3/IMT Atlantique/Université de Nantes, 4 rue Alfred Kastler, BP 20722, 44307, Nantes Cedex 3, France.
Abstract:
The halogen bond is a powerful tool for the molecular design and pushing the limits of its strength is of major interest. Bearing the most potent halogen-bond donor atom, astatine monoiodide (AtI) was recently successfully probed [Nat. Chem. 2018, 10, 428-434]. In this work, we continue the exploration of adducts between AtI and Lewis bases with the tributylphosphine oxide (Bu3 PO) ligand, revealing the unexpected experimental occurrence of two distinct chemical species with 1:1 and 2:1 stoichiometries. The 1:1 Bu3 PO⋅⋅⋅AtI complex is found to exhibit the strongest astatine-mediated halogen bond so far (with a formation constant of 10(4.24±0.35) ). Quantum chemical calculations unveil the intriguing nature of the 2:1 2Bu3 PO⋅⋅⋅AtI adduct, involving a halogen bond between AtI and one Bu3 PO molecular unit plus CH⋅⋅⋅O hydrogen bonds chelating the second Bu3 PO unit.
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