Installing Quaternary Germanium Centers in Sila-Diamondoid Cores via Skeletal Isomerization.

This manuscript describes skeletal isomerization strategies to install one to four quaternary germanium atoms in the sila-adamantane core, in a cluster analogy to precision germanium doping in silicon-germanium alloys. The first strategy embodies an inorganic variant of single-atom skeletal editing, where we use a sila-Wagner-Meerwein bond shift cascade to exchange a peripheral Ge atom with a core Si atom. We can install up to four Ge atoms at the quaternary diamondoid centers based on controlling the Si x Ge y stoichiometry of our precursor. We find that bridgehead Ge centers can be selectively functionalized over bridgehead Si centers in SiGe adamantanes; we use this chemistry in conjunction with scanning tunneling microscopy break-junction (STM-BJ) measurements to show that Si 8 Ge 2 adamantane wires give a 60% increase in single-molecule conductance compared with Si 10 adamantanes. These studies describe the first quantum transport measurements in sila-diamondoid structures, and demonstrate how main-chain Ge doping can be used to increase electronic transmission in sila-diamondoid-based molecular wires.