We drive reversible photoinduced switching of single azobenzene-functionalized molecules isolated in tailored alkanethiolate monolayer matrices on Au{111}. We designed molecular tethers to suppress excited-state quenching from the metal substrate and formed rigid assemblies of single tethered azobenezene molecules in the domains of monolayer to limit steric constraints and tip-induced and stochastic switching effects. Single molecules were reversibly photoisomerized between trans and cis conformations by cycling exposure to visible and UV light. Trans and cis conformations were imaged as high (2.1 +/- 0.3 A) and low (0.7 +/- 0.2 A) protrusions in STM images and were assigned to the on and off states of the molecule, respectively.

A microcantilever, coated with a monolayer of redox-controllable, bistable [3]rotaxane molecules (artificial molecular muscles), undergoes reversible deflections when subjected to alternating oxidizing and reducing electrochemical potentials. The microcantilever devices were prepared by precoating one surface with a gold film and allowing the palindromic [3]rotaxane molecules to adsorb selectively onto one side of the microcantilevers, utilizing thiol-gold chemistry. An electrochemical cell was employed in the experiments, and deflections were monitored both as a function of (i) the scan rate (< or =20 mV s(-1)) and (ii) the time for potential step experiments at oxidizing (>+0.4 V) and reducing (<+0.2 V) potentials. The different directions and magnitudes of the deflections for the microcantilevers, which were coated with artificial molecular muscles, were compared with (i) data from nominally bare microcantilevers precoated with gold and (ii) those coated with two types of control compounds, namely, dumbbell molecules to simulate the redox activity of the palindromic bistable [3]rotaxane molecules and inactive 1-dodecanethiol molecules. The comparisons demonstrate that the artificial molecular muscles are responsible for the deflections, which can be repeated over many cycles. The microcantilevers deflect in one direction following oxidation and in the opposite direction upon reduction. The approximately 550 nm deflections were calculated to be commensurate with forces per molecule of approximately 650 pN. The thermal relaxation that characterizes the device's deflection is consistent with the double bistability associated with the palindromic [3]rotaxane and reflects a metastable contracted state. The use of the cooperative forces generated by these self-assembled, nanometer-scale artificial molecular muscles that are electrically wired to an external power supply constitutes a seminal step toward molecular-machine-based nanoelectromechanical systems (NEMS).

Triarylamines are demonstrated as novel, tunable electroactivated photocatalysts that use dispersion precomplexation to harness the full potential of the visible photon (>4.0 V vs. SCE) in anti-Kasha photo(electro)chemical super-oxidations of arenes.