Department of Chemistry, Tufts University, 62 Talbot Avenue, Medford, MA 02155, USA.
J Phys Condens Matter. 2010 Jul 7;22(26):264006. doi: 10.1088/0953-8984/22/26/264006. Epub 2010 Jun 14.
Thioether molecular rotors show great promise as nanoscale models for exploring the fundamental limits of thermally and electrically driven molecular rotation. By using time-resolved measurements which increase the time resolution of the scanning tunneling microscope we were able to record the dynamics of individual thioether molecular rotors as a function of surface structure, rotor chemistry, thermal energy and electrical excitation. Our results demonstrate that the local surface structure can have a dramatic influence on the energy landscape that the molecular rotors experience. In terms of rotor structure, altering the length of the rotor's alkyl tails allowed the origin of the barrier to rotation to be more fully understood. Finally, time-resolved measurement of electrically excited rotation revealed that vibrational excitation of a C-H bond in the rotor's alkyl tail is an efficient channel with which to excite rotation, and that the excitation is a one-electron process.
硫醚分子转子作为探索热驱动和电驱动分子旋转基本极限的纳米级模型具有很大的应用前景。通过使用时间分辨测量技术,提高了扫描隧道显微镜的时间分辨率,我们能够记录单个硫醚分子转子的动力学,作为表面结构、转子化学、热能和电激发的函数。我们的研究结果表明,局部表面结构对分子转子所经历的能量景观有显著的影响。在转子结构方面,改变转子烷基链的长度可以更全面地了解旋转的障碍起源。最后,电激发旋转的时间分辨测量表明,转子烷基链中 C-H 键的振动激发是一种有效的激发旋转的通道,并且该激发是一个单电子过程。