Conformational influences profoundly impact the performance of organic electronic materials and the reactivity of organic molecules. We recently found that the expected former consideration was uniquely accompanied by the latter. This report describes a surprisingly regioselective bromination that suggests the general use of conformation as a protecting group during complex molecule synthesis. Full Article

The aqueous self-assembly of oligopeptide-flanked pi-conjugated molecules into discrete one-dimensional nanostructures is described. Unique to these molecules is the fact that the pi-conjugated unit has been directly embedded within the peptide backbone by way of a synthetic amino acid with pi-functionality that is compatible with standard Fmoc-based peptide synthesis. The peptide-based molecular design enforces intimate pi-pi communication within the aggregate after charge-screening and self-assembly, making these nanostructures attractive for optical or electronic applications in biological environments. The synthesis and assembly are reported along with spectroscopic and morphological characterization of the new nanomaterials. Full Article

A new strategy to achieve regioselective functionalization of a sterically congested aromatic system driven by conformational demands is described. Electrophilic substitution occurs at the more planarizable subunit without undesired chemistry at mutually reactive sites and without the need for protecting or masking groups that must be manipulated later. Model studies are described to understand this selectivity, and possibilities for the construction of orthogonal, differentially substituted pi-systems of relevance for molecular electronics are demonstrated. Full Article

A comparative study of conjugated polymers derived from the two 10 pi electron circuits of naphthalene and methano[10]annulene is presented. The annulene pi topology allows for a greater degree of intrapolymer charge delocalization, a key structural parameter for enhancing the performance of organic semiconductors. Molecular design and synthesis based upon unusual aromatic cores will enable facile transport properties that would not ordinarily be realized under the 6 pi electron aromatic paradigm. Full Article