Polarity Switching of Charge Transport and Thermoelectricity in Self-Assembled Monolayer Devices

Self‐assembled monolayer devices can exhibit drastically different charge‐transport characteristics and thermoelectric properties despite being composed of isomeric molecules with essentially identical frontier‐orbital energies. This is rationalized by the cooperative electrostatic action of local intramolecular dipoles in otherwise nonpolar species, thus revealing new challenges but also new opportunities for the targeted design of functional building blocks in future nanoelectronics.