Quantitative model for rationalizing solvent effect in noncovalent CH–Aryl interactions† †Electronic supplementary information (ESI) available: Correlation plots; proton and carbon NMR spectra of the molecular balances, and the xyz coordinate of the optimized geometries. See DOI: 10.1039/c5sc03550c

  title={Quantitative model for rationalizing solvent effect in noncovalent CH–Aryl interactions† †Electronic supplementary information (ESI) available: Correlation plots; proton and carbon NMR spectra of the molecular balances, and the xyz coordinate of the optimized geometries. See DOI: 10.1039/c5sc03550c},
  author={Bright U. Emenike and Sara N. Bey and Brianna C. Bigelow and Srinivas V. S. Chakravartula},
  journal={Chemical Science},
  pages={1401 - 1407}
Establishing a linear relationship between CH–aryl interaction energies and the properties of the solvating media. 
13 Citations
Polarisation effects on the solvation properties of alcohols† †Electronic supplementary information (ESI) available: Experimental and computational details. See DOI: 10.1039/c7sc04890d
Alcohol solvents are significantly more polar than expected based on the measured H-bonding properties of monomeric alcohols in dilute solution.
Enantioselective fluorination of homoallylic alcohols enabled by the tuning of non-covalent interactions† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c8sc02223b
Multivariate correlation analysis, including designer π-interaction derived parameters, was applied to the study of the enantioselective fluorination of homoallylic alcohols via chiral anion phase
Measurement of Solvent OH-π Interactions Using a Molecular Balance.
A molecular torsion balance was designed to study and measure OH-π interactions between protic solvents and aromatic surfaces. These specific solvent-solute interactions were measured via their
Stabilizing Fluorine-π Interactions.
A series of N-arylimide molecular balances were designed to study and measure fluorine-aromatic (F-π) interactions, finding the attractive F-π interaction is electrostatically driven and is stronger than other halogen-π interactions.
Cationic CHπ interactions as a function of solvation.
The energy (ΔG) of a cationic CHπ interaction was measured experimentally through the conformational studies of new molecular torsion balances using proton NMR spectroscopy and revealed that electrostatic interaction is the physical origin of the observed conformational preferences in solution.
Study of through-space substituent–π interactions using N-phenylimide molecular balances
Substituent–π interactions associated with aromatic stacking interactions were experimentally measured using a small N-phenylimide molecular balance model system.
Anion-enhanced solvophobic effects in organic solvent.
Specific anion effects were observed that followed the Hofmeister series and enhanced the solvophobic effect up to two-fold.
Synthesis of Molecular Seesaw Balances and the Evaluation of Pyridinium-π Interactions.
A series of molecular seesaw balances 1-5 have been developed to measure the relative strength of pyridinium-π (cation-π) interactions and the effects of the solvent, substituent and counteranion on the ΔG values were elucidated.
The Origin of Chalcogen-Bonding Interactions.
The strongest chalcogen-bonding interactions were found to be at least as strong as conventional H-bonds, but unlike H- bonds, surprisingly independent of the solvent.


Desolvation and substituent effects in edge-to-face aromatic interactions.
Experimental measurements of aromatic edge-to-face interaction energies in both molecular torsion balances and supramolecular zipper complexes can be reliably estimated using a simple electrostatic
A molecular balance for measuring aliphatic CH-π interactions.
A series of conformationally flexible bicyclic N-arylimides were employed as molecular balances to study the weak aliphatic CH-π interaction between alkyl and arene groups. The formation of
Quantification of CH···π interactions: implications on how substituent effects influence aromatic interactions.
Attractive interactions between a substituted benzene ring and an α-substituted acetate group were determined experimentally by using the triptycene model system. The attractive interaction
Conformational equilibria of N,N-dimethylsuccinamic acid and its lithium salt as a function of solvent.
The conformational preferences of N,N-dimethylsuccinamic acid and its Li(+) salt were estimated by comparing the respective experimental NMR vicinal proton-proton coupling constants to semiempirical
Strength of molecular complexation of apolar solutes in water and in organic solvents is predictable by linear free energy relationships: a general model for solvation effects on apolar binding
La stabilite d'un complexe d'inclusion forme par un cyclophane macrobicyclique, compose hote et le pyrene est etudiee dans l'eau et dans differents solvants organiques, de differentes polarites.
Unraveling the Role of Alkyl F on CH-π Interactions and Uncovering the Tipping Point for Fluorophobicity.
Findings indicate that fluorine's polarizing ability does enhance CH-π binding and depends on molecular orientation, and when the terminal end of the alkyl group is completely fluorinated, the balance tips toward fluorophobicity and assumes an unusual constrained conformation.
Theoretical Study of Alkyl-π and Aryl-π Interactions. Reconciling Theory and Experiment
Quantum mechanical and quantum mechanical/molecular mechanical calculations in conjunction with continuum solvation models have been used to analyze CH-π interactions in model systems of aryl- and
Molecular Balances Based on Aliphatic CH-π and Lone-Pair-π Interactions.
Calculations suggest strategies to selectively isolate the folded form by increasing the strength of the attractive CH··π interaction or removing the lone-pair···π repulsion.
Seeing through solvent effects using molecular balances
The study of molecular interactions is often complicated by solvent effects. Here we have used a series of 11 synthetic molecular balances to measure solvent and substituent effects on the positions
Quantifying Solvophobic Effects in Nonpolar Cohesive Interactions.
Synthetic molecular balances are used to measure solvent effects on aromatic, aliphatic, and fluorous nonpolar interactions to establish ced as a readily accessible, quantitative descriptor of solvophobic association in a range of chemical contexts.