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Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
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Engineering supramolecular helical assemblies via interplay between carbon(sp) tetrel and halogen bonding
Burcu Dedeoglu1, Ayşe Gül Gürek1, Yunus Zorlu1
1Department of Chemistry, Gebze Technical University, Gebze, Kocaeli, Turkey. menafayhan@gtu.edu.tr.
Physical Chemistry Chemical Physics : PCCP
|April 11, 2023
Summary
Researchers designed novel scaffolds using bromine and cyano groups to control noncovalent interactions, successfully forming diverse helical supramolecular structures. This work advances crystal engineering and materials science by highlighting the importance of sigma-hole accessibility.
Area of Science:
- Supramolecular Chemistry
- Crystal Engineering
- Materials Science
Background:
- Designing supramolecular helical structures is challenging due to the complexity of controlling competitive noncovalent forces.
- Scaffolds decorated with cyano (-C≡N) and bromine (-Br) groups offer potential for multiple noncovalent interactions.
Purpose of the Study:
- To investigate the formation of supramolecular helical assemblies using novel scaffolds functionalized with -C≡N and -Br groups.
- To elucidate the role of specific noncovalent interactions, including Csp-tetrel bonding and halogen bonding, in directing helical assembly.
- To understand how the geometric accessibility of sigma holes influences dominant interactions and assembly outcomes.
Main Methods:
- Synthesis of three scaffolds (1a, 1b, 1c) featuring -C≡N and -Br groups.
- X-ray diffraction analysis to determine crystal packing and identify dominant intermolecular interactions.
- Computational analysis, including MEP (Molecular Electrostatic Potential) calculations, to assess interaction nature and strength.
Main Results:
- X-ray analyses revealed distinct crystal packing dominated by specific interactions: Br⋯C≡N Csp-tetrel bonding in 1a, Br⋯π and Br⋯N in 1b, and Br⋯Br in 1c.
- These interactions led to the formation of different helical assemblies: achiral P/M in 1a, chiral M in 1b, and achiral P/M in 1c.
- Csp-tetrel bonding in 1a, despite being considered weak, proved to be the strongest interaction, emphasizing the critical role of sigma-hole accessibility.
Conclusions:
- The geometric accessibility of sigma holes significantly influences the dominant noncovalent interactions and dictates the type of helical assembly formed.
- This study demonstrates the successful rational design of complex helical supramolecular structures by controlling halogen bonding and Csp-tetrel bonding.
- Findings provide a foundation for the future design of advanced self-assembled materials for applications in crystal engineering, organic electronics, sensors, and medicinal chemistry.
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