Journal of the American Chemical Society, Vol.136, No.25, 8871-8874, 2014
Rotation of a Bulky Triptycene in the Solid State: Toward Engineered Nanoscale Artificial Molecular Machines
We report the design and dynamics of a solid-state molecular rotor with a large triptycene rotator. With a cross-section and surface area that are 2 and 3 times larger than those of the phenylene rotators previously studied in the solid state, it is expected that van der Waals forces and steric hindrance will render the motion of the larger triptycene more difficult. To address this challenge, we used a rigid and shape-persistent stator in a dendritic structure that reaches ca. 3.6 nm in length. Using variable-temperature solid-state H-2 NMR spectroscopy, we determined a symmetric three-fold rotational potential with a barrier of 10.2 kcal/mol and a pre-exponential factor of 1.1 X 10(10) s(-1), which correspond to ca. 4600 Brownian jumps per second in the solid state at 300 K.