Molecular Dynamics of Steroidal Rotors Probed by Theoretical, Spectroscopic and Dielectric Methods

Abstract

Our study focuses on molecular rotors with fast‐moving rotators and their potential applications in the development of new amphidynamic crystals. Steroidal molecular rotors with a dipolar fluorine‐substituted phenyl group as the rotator were synthesized and characterized. Three different rotors were investigated with varying numbers of fluorine atoms. A comprehensive analysis was performed using vibrational spectroscopy (Raman, FT‐IR), electronic circular dichroism (ECD), and dielectric response to understand the behavior of the investigated model rotors. The results were supported by theoretical calculations using Density Functional Theory (DFT) methods. The angle‐dependent polarized Raman spectra confirmed the crystallinity of the samples. Nearly frequency and temperature‐independent permittivity suggest low‐frequency librational motion of stators. An in‐depth analysis of ECD spectra revealed high conformational flexibility in solution, resulting in low ECD effects, while in the solid‐state with restricted rotation, significant ECD effects were observed. These findings shed light on the conformational behavior and potential applications of the studied steroidal molecular rotors.