We have developed a program to show how well-defined stereoelectronic interactions within molecules can be used to control self-assembly and emergent macromolecular behavior. Our latest results establish, through X-ray crystallography and high-level computation, that cyclic beta-aminoketones are useful molecular constructs for these studies. In the solid state, through-bond communication between donor and acceptor orbitals is reflected by understandable but dramatic changes in bond lengths, bond angles, and conformational preferences. When the right functional groups are then introduced to such "donor-sigma-acceptor" scaffolds, the molecules can form infinite and ordered networks in solution and the solid state. While the behavior is complex, it does respond to changes in molecular structure in ways that draw relationships between through-bond interactions and bulk properties. 1-Aza-adamantanetriones bearing naphthylamide groups have recently been prepared and are illustrative; the molecules aggregate in organic solvents at exceedingly low concentrations, and form gels at ~ 1 mM in toluene and benzene. The assemblies can be monitored for the first time by fluorescence spectroscopy and dynamic light scattering. The latest synthetic approaches for preparing the first differentially functionalized and even chiral molecules for ongoing studies will be reported.