Mechanical Manipulation of Quantum Interference in Single-Molecule Junctions.

Mechanosensitive molecular junctions, where conductance is sensitive to an applied stress such as force or displacement, are a class of nanoelectromechanical systems unique for their ability to exploit quantum mechanical phenomena. Most studies so far relied on reconfiguration of the molecule-electrode interface to impart mechanosensitivity, but this approach is limited and, generally, poorly reproducible. Alternatively, devices that exploit conformational flexibility of molecular wires have been recently proposed. The mechanosensitive properties of molecular wires containing the 1,1'-dinaphthyl moiety are presented here. Rotation along the chemical bond between the two naphthyl units is possible, giving rise to two conformers (transoid and cisoid) that have distinctive transport properties. When assembled as single-molecule junctions, it is possible to mechanically trigger the transoid to cisoid transition, resulting in an exquisitely sensitive mechanical switch with high switching ratio (> 102). Theoretical modeling shows that charge reconfiguration upon transoid to cisoid transition is responsible for the observed behavior, with generation and subsequent lifting of quantum interference features. These findings expand the experimental toolbox of molecular electronics with a novel chemical structure with outstanding electromechanical properties, further demonstrating the importance of subtle changes in charge delocalization on the transport properties of single-molecule devices.

Large Mechanosensitive Thermoelectric Enhancement in Metallo-Organic Magnetic Molecules.

Organic materials are promising candidates for thermoelectric cooling and energy harvesting at room temperature. However, their electrical conductance (G) and Seebeck coefficient (S) need to be improved to make them technologically competitive. Therefore, radically new strategies need to be developed to tune their thermoelectric properties. Here, we demonstrate that G and S can be tuned mechanically in paramagnetic metallocenes, and their thermoelectric properties can be significantly enhanced by the application of mechanical forces. With a 2% junction compression, the full thermoelectric figure of merit is enhanced by more than 200 times. We demonstrate that this is because spin transport resonances in paramagnetic metallocenes are strongly sensitive to the interaction between organic ligands and the metal center, which is not the case in their diamagnetic analogue. These results open a new avenue for the development of organic thermoelectric materials for cooling future quantum computers and generating electricity from low-grade energy sources.