Substituent effects on aromatic stacking interactions

Synthetic supramolecular zipper complexes have been used to quantify substituent effects on the free energies of aromatic stacking interactions. The conformational properties of the complexes have been characterised using NMR spectroscopy in CDCl3, and by comparison with the solid state structures o...

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Published inOrganic & biomolecular chemistry Vol. 5; no. 7; pp. 1062 - 1080
Main Authors Cockroft, Scott L., Perkins, Julie, Zonta, Cristiano, Adams, Harry, Spey, Sharon E., Low, Caroline M. R., Vinter, Jeremy G., Lawson, Kevin R., Urch, Christopher J., Hunter, Christopher A.
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 01.01.2007
Subjects
Aniline Compounds - chemical synthesis
Aniline Compounds - chemistry
Binding Sites
Chemistry
Chemistry, Organic
Hydrogen Bonding
Magnetic Resonance Spectroscopy - methods
Models, Chemical
Models, Molecular
Molecular Structure
Phthalic Acids - chemical synthesis
Phthalic Acids - chemistry
Physical Sciences
Science & Technology
Sensitivity and Specificity
Stereoisomerism
PI-PI-INTERACTIONS
ARENE INTERACTIONS
FACE-TO-FACE
DOUBLE-MUTANT CYCLES
MOLECULAR TORSION BALANCE
POLAR INTERACTIONS
CHARGE-TRANSFER
MODEL COMPOUNDS
INTERMOLECULAR INTERACTIONS
AQUEOUS-SOLUTION
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Summary:Synthetic supramolecular zipper complexes have been used to quantify substituent effects on the free energies of aromatic stacking interactions. The conformational properties of the complexes have been characterised using NMR spectroscopy in CDCl3, and by comparison with the solid state structures of model compounds. The structural similarity of the complexes makes it possible to apply the double mutant cycle method to evaluate the magnitudes of 24 different aromatic stacking interactions. The major trends in the interaction energy can be rationalised using a simple model based on electrostatic interactions between the pi-faces of the two aromatic rings. However, electrostatic interactions between the substituents of one ring and the pi-face of the other make an additional contribution, due to the slight offset in the stacking geometry. This property makes aromatic stacking interactions particularly sensitive to changes in orientation as well as the nature and location of substituents.
Bibliography:researchfish
ISSN:1477-0520
1477-0539
DOI:10.1039/b617576g