We report a strategy for using steric direction to construct self-assembling metal chalcogenolate superstructures comprised of either 1- or 2-dimensional subunits.  Reactions between sulfhydryl and metal ions (Ag+, Cu+, and Cd+) are harnessed and directed by an associated molecular sidegroup, producing inorganic materials of controlled dimensionality mediated by the shape of and interactions between the sidegroups.  Sterically directed chalcogenolates (SDCs) are hierarchically organized materials with bonding configurations and porosity defined by the molecular sidegroups.  Bulky groups crowd the metal coordination sphere and direct the material into a superstructure of 1-dimensional wires that extend by chain elongation whereas compact sidegroups produce extended 2-dimensional laminar materials.  We employ thiol-derivatized ferrocene, carborane, and diamondoids to investigate how altering molecular geometry, intermolecular forces, and chemical functionality cause the SDC system to respond at atomic-, supramolecular-, and macroscales.  Single-crystal X-ray diffraction solutions for a variety of SDCs provide the basis for design principles useful for developing new semiconducting, superconducting, superionic, and topological insulating materials.

Sterically directed chalcogenides: Self-assembling superstructures of <i>n</i>-dimensional materials

246th National Meeting (2013)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.

Sterically directed chalcogenides: Self-assembling superstructures of n-dimensional materials