Thermodynamic evaluation of aromatic CH/π interactions and rotational entropy in a molecular rotor
- Pérez-Estrada, S. 2
- Rodríguez-Molina, B. 2
- Xiao, L. 2
- Santillan, R. 1
- Jiménez-Osés, G. 2
- Houk, K.N. 2
- Garcia-Garibay, M.A. 2
-
1
Instituto Politécnico Nacional
info
-
2
University of California Los Angeles
info
ISSN: 0002-7863
Año de publicación: 2015
Volumen: 137
Número: 6
Páginas: 2175-2178
Tipo: Artículo
Otras publicaciones en: Journal of the American Chemical Society
Resumen
A molecular rotor built with a stator formed by two rigid 9β-mestranol units having a 90° bent angle linked to a central phenylene rotator has an ideal structure to examine aromatic CH/π interactions. Energies and populations of the multiple solution conformations from quantum-mechanical calculations and molecular dynamics simulations were combined with variable-temperature (VT) 1H NMR data to establish the enthalpy of this interaction and the entropy associated with rotation about a single bond. Rotational dynamics in the solid state were determined via VT cross-polarization magic-angle spinning 13C NMR spectroscopy. © 2015 American Chemical Society.