The Bicyclo[2.2.2]octane Motif: A Class of Saturated Group 14 Quantum Interference Based Single-Molecule Insulators

The electronic transmission through σ-conjugated molecules can be fully suppressed by destructive quantum interference, which makes them potential candidates for single-molecule insulators. The first molecule with clear suppression of the single-molecule conductance due to σ-interference was recently found in the form of a functionalized bicyclo[2.2.2]­octasilane. Here we continue the search for potential single-molecule insulators based on saturated group 14 molecules. Using a high-throughput screening approach, we assess the electron transport properties of the bicyclo[2.2.2]­octane class by systematically varying the constituent atoms between carbon, silicon, and germanium, thus exploring the full chemical space of 771 different molecules. The majority of the molecules in the bicyclo[2.2.2]­octane class are found to be highly insulating molecules. Though the all-silicon molecule is a clear-cut case of σ-interference, it is not unique within its class and there are many potential molecules that we predict to be more insulating. The finding of this class of quantum interference based single-molecule insulators indicates that a broad range of highly insulating saturated group 14 molecules are likely to exist.