Evolution of Strategies for Self‐Assembly and Hookup of Molecule‐Based Devices

: Strategies for self-assembling molecule-based devices are considered in terms of current chemical issues whose resolution appears critical to efficient connection and addressing of electronically active molecules between electrodes. We discuss issues related to the type and shape of the molecules, chemical bonding at junctions, molecular lengths and electrode gap matching, molecular alignment at electrodes, chemistry of deposited metal contacts, and the doping of molecular conductors. Examples of each of these aspects is given using fully conjugated molecules, constituted from rigid rod phenylene-ethynylene units, self-assembled onto metal and semiconductor surfaces.