Much of the motivation for developing molecular electronic devices is the prospect of achieving novel electronic functions by varying molecular structure. We describe a "building block" approach for molecular junctions resulting in one, two or three nanometer-thick molecular layers in a commercially proven junction design. A single layer of anthraquinone between carbon electrodes provides a tunnel device with applications in electronic music, and a second layer of a thiophene derivative yields a molecular rectifier with quite different audio characteristics. A third layer of lithium benzoate produces a redox-active device with possible applications in non-volatile memory devices or on-chip energy storage. The building block approach forms a basis for "rational design" of electronic functions, in which layers of varying structure produce distinct and desirable electronic behaviours.