On the possibility to accelerate the thermal isomerizations of overcrowded alkene-based rotary molecular motors with electron-donating or electron-withdrawing substituents

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Abstract

We employ computational methods to investigate the possibility of using electron-donating or electron-withdrawing substituents to reduce the free-energy barriers of the thermal isomerizations that limit the rotational frequencies achievable by synthetic overcrowded alkene-based mol. motors. Choosing as ref. systems one of the fastest motors known to date and two variants thereof, we consider six new motors obtained by introducing electron-donating methoxy and dimethylamino or electron-withdrawing nitro and cyano substituents in conjugation with the central olefinic bond connecting the two (stator and rotator) motor halves. Performing d. functional theory calcns., we then show that electron-donating (but not electron-withdrawing) groups at the stator are able to reduce the already small barriers of the ref. motors by up to 18 kJ mol-1. This result outlines a possible strategy for improving the rotational frequencies of motors of this kind. Furthermore, exploring the origin of the catalytic effect, it is found that electron-donating groups exert a favorable steric influence on the thermal isomerizations, which is not manifested by electron-withdrawing groups. This finding suggests a new mechanism for controlling the crit. steric interactions of these motors. [on SciFinder(R)]

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Oruganti, B., & Durbeej, B. (2016). On the possibility to accelerate the thermal isomerizations of overcrowded alkene-based rotary molecular motors with electron-donating or electron-withdrawing substituents. Journal of Molecular Modeling, 22(9). https://doi.org/10.1007/s00894-016-3085-y

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