Electrostatically enhanced FF interactions through hydrogen bonding, halogen bonding and metal coordination: an ab
Antonio Bauzá1, Antonio Frontera1
1Department of Chemistry Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, 07122 Palma (Baleares), Spain. toni.frontera@uib.es.
Physical Chemistry Chemical Physics : PCCP
|July 13, 2016
Summary
This study explores how hydrogen bonding, halogen bonding, and metal coordination influence fluorine-fluorine (FF) interactions in aromatic systems. Findings reveal cooperative effects enhancing these interactions in solid-state chemistry.
Area of Science:
- Computational Chemistry
- Supramolecular Chemistry
- Materials Science
Background:
- Fluorine-substituted aromatic rings are crucial in pharmaceuticals and materials.
- Non-covalent interactions, including hydrogen and halogen bonding, play significant roles in molecular recognition and self-assembly.
- Understanding fluorine-fluorine (FF) interactions is essential for designing novel functional molecules and materials.
Purpose of the Study:
- To investigate the enhancement of FF interactions in fluorine-substituted aromatic systems.
- To analyze the cooperative effects between FF interactions and hydrogen/halogen bonding or metal coordination.
- To explore the role of FF interactions in solid-state chemistry.
Main Methods:
- Quantum chemical calculations using the RI-MP2/def2-TZVPD level of theory.
- Utilized aromatic compounds: 4-fluoropyridine, 4-fluorobenzonitrile, 3-(4-fluorophenyl)propiolonitrile, and their meta derivatives.
- Employed hydrogen bond donor (HF), halogen bond donor (IF), and coordination metal (Ag(I)).
- Conducted a Cambridge Structural Database (CSD) search.
- Applied Bader's theory of 'atoms in molecules' for analysis.
Main Results:
- Hydrogen bonding, halogen bonding, and Ag(I) coordination effectively enhance FF interactions involving aromatic fluorine atoms.
- HF can act as an electron-rich fluorine donor, establishing FF interactions.
- CSD search revealed significant examples of FF interactions in solid-state structures.
- Cooperative effects between FF interactions and other non-covalent interactions were observed and quantified.
Conclusions:
- Non-covalent interactions significantly modulate FF interactions in fluorine-substituted aromatics.
- Cooperative effects are crucial for understanding the assembly and properties of fluorinated compounds in the solid state.
- The findings provide insights for the rational design of materials and molecules utilizing fluorine's unique properties.
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