A pentiptycene-derived molecular brake: photochemical E→Z and electrochemical Z→E switching of an enone module.
The synthesis and brakelike performance of a new molecular system (1) consisting of a pentiptycene rotor and a 2-methyleneindanone brake are reported. The rotation kinetics of the rotor was probed by both variable-temperature (1)H and (13)C NMR spectroscopy and DFT calculations, and the switching between the brake-on and brake-off states was conducted by a combination of photochemical and electrochemical isomerization. Because of the greater steric hindrance between the rotor and the brake units in the Z form ((Z)-1) than in the E form ((E)-1), rotation of the rotor is slowed down 500-fold at room temperature (298 K) on going from (E)-1 to (Z)-1, corresponding to the brake-off and brake-on states, respectively. The (E)-1→(Z)-1 photoisomerization in acetonitrile is efficient and reaches an (E)-1/(Z)-1 ratio of 11:89 in the photostationary state upon excitation at 290 nm, attributable to a much larger isomerization quantum efficiency for (E)-1 versus (Z)-1. An efficient (Z)-1→(E)-1 isomerization (96%) was also achieved by electrochemical treatment through the radical anionic intermediates. Consequently, the reversibility of the E-Z switching of 1 is as high as 85%. The repeated E-Z switching of 1 with alternating photochemical and electrochemical treatments is also demonstrated.
Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan.
Ying-Chen
YC
Chen
Wei-Ting
WT
Sun
Hsiu-Feng
HF
Lu
Ito
I
Chao
Guan-Jhih
GJ
Huang
Ying-Chih
YC
Lin
Shou-Ling
SL
Huang
Hsin-Hau
HH
Huang
Yan-Duo
YD
Lin
Jye-Shane
JS
Yang