Computational study of the structure, dynamics, and photophysical properties of conjugated polymers and oligomers under nanoscale confinement

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.