Computational simulations were used to investigate the dynamics and resulting structures of several paraphenylenevinylene (PPV) based polymers and oligomers (PPV, 2-methoxy-5-(2'-ethyl-hexyloxy)-p-phenylenevinylene -> MEH-PPV and 2,5,2',5'-tetrahexyloxy-7,8'-dicyano-p-phenylenevinylene -> CN-PPV). The results show how the morphology and structure are controlled to a large extent by the nature of the solute-solvent interactions in the initial solution-phase preparation. Secondary structural organization is induced by using the solution-phase structures to generate solvent-free single molecule nanoparticles. Isolation of these single molecule nanostructures from microdroplets of dilute solution results in the formation of electrostatically oriented nanostructures at a glass surface. Our structural modeling suggests that these oriented nanostructures consist of folded PPV conjugated segments with folds occurring at tetrahedral defects (sp(3) C-C bonds) within the polymer chain. This picture is supported by detailed experimental fluorescence and scanning probe microscopy studies. We also present results from a fully quantum theoretical treatment of these systems which support the general conclusion of structure-mediated photophysical properties.