Thermodynamic Evaluation of Aromatic CH/π Interactions and Rotational Entropy in a Molecular Rotor
Thermodynamic Evaluation of Aromatic CH/π Interactions and Rotational Entropy in a Molecular Rotor
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DOI：
10.1021/ja512053t
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发表时间：
2015-02-18
影响因子：
15
通讯作者：
Garcia-Garibay, Miguel A.
中科院分区：
文献类型：
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作者：
Perez-Estrada, Salvador;Rodriguez-Molina, Braulio;Garcia-Garibay, Miguel A.
由两个刚性9 β-mestranol单元形成的定子与中心亚苯基旋转体连接形成的分子转子具有理想的结构，以检查芳香CH/p相互作用。从量子力学计算和分子动力学模拟的多个解决方案的构象的能量和人口与变温（VT）H-1 NMR数据相结合，以建立这种相互作用的焓和熵与旋转有关的单键。通过VT交叉极化魔角旋转C-13 NMR光谱测定固态中的旋转动力学。
A molecular rotor built with a stator formed by two rigid 9 beta-mestranol units having a 90 degrees bent angle linked to a central phenylene rotator has an ideal structure to examine aromatic CH/p interactions. Energies and populations of the multiple solution conformations from quantum-mechanical calculations and molecular dynamics simulations were combined with variable-temperature (VT) H-1 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 C-13 NMR spectroscopy.