Steric and Substrate Mediation of Polymers Formed within Single Molecular Layers

Abstract

The fabrication of well-defined interfacial structures has been recently facilitated by incorporating diacetylenic structures within spontaneously formed monolayer assemblies. Photoinduced polymerization within these single molecular layers provides a robust system for interfacial design that can be controlled using phototemplating. In this paper, we examine the control of molecular structure within this single molecular layer by introducing internal and external perturbations to the monolayer fabrication process. Internal steric perturbations are assessed by incorporation of an ester moiety below the polymer backbone. Direct comparison of monolayer structures formed using analogous precursors with and without the ester functionality indicates significant disruption in the alkyl crystallinity in the region below the polymer backbone. Despite the considerable constraints on the structural order required for successful polymerization, this steric disruption does not appear to significantly limit the polymer...