A method for selectively assembling a molecular device on a substrate comprises contacting the first substrate with a solution containing molecular devices; impeding bonding of the molecular devices to the substrate such that application of a voltage potential to the substrate results in assembly of the molecular device on the substrate at a rate that is at least 1.5 times the rate of assembly of the molecular device on a voltage-neutral substrate; and applying a voltage potential to the substrate so as to cause the molecular devices to assemble on the substrate. A nanoscale computing device is described that includes a substrate, a pair of conductive input/output electrodes carried on this substrate and disposed in spaced-apart relationship and a substantially disordered assembly of nanowires formed on the substrate in a region between the electrodes, thereby forming at least one programmable conductive pathway between the pair of electrodes.