Allosteric Regulation of the Rotational Speed in a Light-Driven Molecular Motor

作者：Faulkner Adele; van Leeuwen Thomas; Feringa Ben L^*; Wezenberg Sander J^*

来源：Journal of the American Chemical Society, 2016, 138(41): 13597-13603.

DOI：10.1021/jacs.6b06467

The rotational speed of an overcrowded alkene-based molecular rotary motor, having an integrated 4,5-diazafluorenyl coordination motif, can be regulated allosterically via the binding of metal ions. DFT calculations have been used to predict the relative speed of rotation of three different (i.e., zinc, palladium, and platinum) metal dichloride complexes. The photochemical and thermal isomerization behavior of these complexes has been studied in detail using UV-vis and H-1 NMR spectroscopy. Our results confirm that metal coordination induces a contraction of the diazafluorenyl lower half, resulting in a reduction of the steric hindrance in the "fjord" region of the molecule, which causes an increase rotational speed. Importantly, metal complexation can be accomplished in situ and is found to be reversible upon the addition of a competing ligand. Consequently, the rotational behavior of these molecular motors can be dynamically controlled with chemical additives.

• 出版日期2016-10-19