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A Bidentate Antimony Pnictogen Bonding Host System.

J Louis Beckmann1, Jonas Krieft1, Yury V Vishnevskiy1

  • 1Chair of Inorganic and Structural Chemistry, Center for Molecular Materials CM2 Faculty of Chemistry, Bielefeld University, Universitätsstrasse 25, 33615, Bielefeld, Germany.

Angewandte Chemie (International Ed. in English)
|September 29, 2023
PubMed
Summary

Researchers developed a novel antimony-based host system for pnictogen bonding. This system effectively complexes with various Lewis bases and anions, showcasing antimony

Keywords:
AntimonyLewis AcidMolecular RecognitionNon-Covalent InteractionsPnictogen Bond

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Area of Science:

  • Supramolecular Chemistry
  • Organometallic Chemistry
  • Materials Science

Background:

  • Pnictogen bonding, a non-covalent interaction involving pnictogen elements (Group 15), is an emerging area in supramolecular chemistry.
  • Exploring Lewis acidic pnictogen centers as host components for guest complexation remains largely underdeveloped.
  • Antimony(III) sites offer a promising, yet underexplored, avenue for creating novel pnictogen bonding interactions.

Purpose of the Study:

  • To synthesize and characterize a novel bidentate pnictogen bonding host system utilizing a 1,8-diethynylanthracene scaffold.
  • To investigate the Lewis acidic properties of a newly established C≡C-Sb(C2F5)2 unit for complexing Lewis basic and anionic guests.
  • To explore the potential of antimony(III) as a representative pnictogen bonding donor.

Main Methods:

  • Synthesis via selective tin-antimony exchange reaction.
  • Characterization using NMR spectroscopy, X-ray diffraction, and elemental analysis.
  • Computational studies including Density Functional Theory (DFT), Quantum Theory of Atoms in Molecules (QTAIM), and Independent Gradient Model (IGM) analysis.

Main Results:

  • Successful synthesis of a novel host system featuring a C≡C-Sb(C2F5)2 moiety.
  • Demonstrated complexation capabilities with halide anions (Cl-, Br-, I-), dimethyl chalcogenides (Me2Y, Y=O, S, Se, Te), and nitrogen heterocycles (pyridine, pyrimidine).
  • Detailed insights into adduct formation and the electronic nature of E···Sb-CF bonds through experimental and computational analyses.

Conclusions:

  • The synthesized antimony(III)-based system functions effectively as a Lewis acidic host for pnictogen bonding.
  • Antimony(III) sites are viable representatives for exploring pnictogen bonding donors.
  • This study expands the scope of pnictogen bonding interactions and host-guest chemistry.