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Triple-Pnictogen Bonding as a Tool for Supramolecular Assembly
Shiva Moaven1, Miranda C Andrews1, Thomas J Polaske2
1Department of Chemistry and Biochemistry , Texas Tech University , 1204 Boston Avenue , Lubbock , Texas 79409-1061 , United States.
Inorganic Chemistry
|November 14, 2019
Summary
Researchers explored simultaneous triple pnictogen bonding around antimony using X-ray crystallography and NMR. Designing a rigid arylethynyl ligand enabled simultaneous binding, overcoming limitations of negative cooperativity in supramolecular assembly.
Area of Science:
- Supramolecular Chemistry
- Inorganic Chemistry
- Crystallography
Background:
- Pnictogen bonding is an important non-covalent interaction.
- Antimony (Sb) can act as a Lewis acid in pnictogen bonding.
- Achieving simultaneous multiple pnictogen bonds is challenging.
Purpose of the Study:
- To investigate the simultaneous formation of three pnictogen bonds around a single antimony center.
- To design and test a complementary arylethynyl (AE) ligand for efficient triple pnictogen bonding.
- To understand the role of cooperativity in multiple pnictogen bond formation.
Main Methods:
- X-ray crystallography to determine molecular structures.
- Solution Nuclear Magnetic Resonance (NMR) spectroscopy to study binding interactions.
- Computational chemistry (e.g., DFT calculations) to analyze bonding and cooperativity.
Main Results:
- Successful exploration of simultaneous triple pnictogen bonding around an antimony vertex.
- Demonstration that a rigid, prearranged arylethynyl ligand is crucial for simultaneous binding.
- Identification of negative cooperativity with simple pyridyl acceptors limiting triple bonding.
- Evidence that positive cooperativity, designed into the acceptor ligand, overcomes these limitations.
Conclusions:
- Simultaneous triple pnictogen bonding around antimony is achievable with appropriate ligand design.
- Ligand rigidity and prearrangement are key factors for overcoming negative cooperativity.
- Designing for positive cooperativity in acceptor ligands is essential for efficient multiple pnictogen bond formation.
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