Template-synthesized nanostructure morphology influenced by building block structureElectronic supplementary information (ESI) available: Synthesis of 3-(2-ethyl)hexylthiophene, 1-bromo-2-(2-ethoxy)ethoxyethane, and 3-(2-(2-(2-ethoxy)ethoxy)ethoxy)methylthiophene; and additional images. See DOI: 10.1039/c0jm02651d

We report the synthesis and characterization of a series of nanostructures and determine whether several distinct types of building blocks can be fashioned into linear nanostructures using hard-templates and electrochemical methods. We determine the aspects of molecular structure that influence morphology and propose a mechanism whereby morphology changes as a function of building block. We show how hydrophobic side-chains, such as 3-hexyl and 3-(2-ethyl)hexyl, can be used to prepare nanostructures with a geometry that is different from the shape of the template from which they derive. These nanostructures exhibit collapsed, nonlinear, and nonrigid shapes as observed by SEM and TEM. Hydrophilic side-chains such as 3-(2-(2-(2-ethoxy)ethoxy)ethoxy)methyl and 3-(hydroxy)methyl lead to linear nanostructures. We are also able to prepare linear nanostructures composed of the narrow HOMO-LUMO gap heterocycles selenophene and thieno[3,2- b ]thiophene. The results open up many new opportunities for preparing nanostructures with greater complexity, functionality, and distinct optical properties that are imparted by their building block. In this study we synthesize and characterize a series of nanostructures and determine whether several distinct types of building blocks, including those with various side-chains and those with various π-conjugated cores, can be fashioned into nanostructures using hard-templates and electrochemical methods.