Bulk silicon’s semiconducting properties has led to silicon being the defining material of the 21st century as seen in its widespread uses in modern technology. As electronics become increasingly smaller and more powerful, there has been much interest in exploring the behavior of silicon at the nanoscale. While silicon nanoparticles have promising applications as qubit hosts, bioimaging agents or lithium anodes, the heterogeneity of nanoparticle sizes, shapes and surfaces mask the elucidation of structure property relationships. By synthesizing silicon molecules from a “bottom-up” synthetic approach, atomic level precision is obtained and structure-property relationships in silicon nanoparticles are established. Inspired by the bulk silicon lattice, we sought to synthesize well-defined silicon clusters we have coined “sila-diamondoids”. Here, we report the optimization of the AlCl3 catalyzed rearrangement towards sila-adamantane by adjusting conditions such as solvent, temperature, catalyst loading and concentration. This optimization has allowed us to synthesize sila-adamantane on gram scales. We further demonstrated that sila-adamantane can be used as a building block material resulting in functionalized derivatives at the 1, 1,3 and 1,3,5,7 positions. Next, we established a scope of SiAd functionalized with aurophillic linker groups (-CH2SMe) to be studied in the context of single molecule electronic studies. We developed methods to functionalize SiAd(CH2SMe)2 further and installed a scope of electronegative substituents at site specific locations about the cluster core. We intend to investigate the effects of electronegative substituents on the electronic environment of SiAds and how they relate to charge transport behavior. In efforts to expand the use of SiAd as a material of interest, we dimerized two SiAd clusters between a linear oligosilane chain to form a type of oligosilane linked dumbbell structure. We then established a scope of oligosilane dumbbells with varying lengths or varying cluster sizes to probe their relative effects on optical properties. Finally, we were able to synthesize a novel silicon analogue of carbon trishomocubane cubane cluster, which we have dubbed “sila-trishomocubane”. Investigation of the mechanism of formation of sila-trishomocubane allowed us to gain valuable insight into the driving forces of oligosilane isomerizations.