Dynamics of a Molecular Rotor Exhibiting Local Directional Rotational Preference within Each Enantiomer,The Journal of Physical Chemistry A

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Dynamics of a Molecular Rotor Exhibiting Local Directional Rotational Preference within Each Enantiomer
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2021-03-05 , DOI: 10.1021/acs.jpca.0c08476
Kirill Nikitin ₁ , Yannick Ortin ₁ , Michael J. McGlinchey ₁

Affiliation

Directional internal rotation in molecular systems, generally controlled by chirality, is known to occur in natural and artificial systems driven by light or fueled chemically, but spontaneous directional molecular rotation is believed to be forbidden. We have designed a molecular rotor, whereby ferrocene and triptycene linked by a methylene bridge provide two rotational degrees of freedom. On the basis of experimental observations, in conjunction with computational data, we show that the two different modes of rotation are strongly coupled and the spatial orientation of the bistable ferrocene moiety controls the barrier to its own rotation about the triptycene axis. It is proposed that the barrier to clockwise 120° rotation across each individual triptycene blade is lower in the M-enantiomer and for counterclockwise 120° rotation, it is lower in its P-counterpart. These findings demonstrate the possibility of locally preferred thermal directional intramolecular rotation for each dynamically interconverting enantiomer.

中文翻译：

在每个对映异构体中表现出局部方向性旋转偏好的分子转子的动力学。

已知通常由手性控制的分子系统中的定向内部旋转发生在由光或化学燃料驱动的天然和人工系统中，但是人们认为自发的定向分子旋转是被禁止的。我们设计了一个分子转子，通过亚甲基桥连接的二茂铁和三茂铁提供了两个旋转自由度。在实验观察的基础上，结合计算数据，我们显示出两种不同的旋转模式是强耦合的，并且双稳态二茂铁部分的空间方向控制了其绕三并四烯轴旋转的势垒。建议在每个M梯形叶片上顺时针旋转120°的障碍在M中较低-对映体，逆时针旋转120°，其P相向部分较低。这些发现证明了每种动态互变对映异构体局部优选的热定向分子内旋转的可能性。

更新日期：2021-03-18

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