^(a)Display requires a Javascript-enabled Web browser, 3D models and 2D diagrams being invoked by clicking on any of the labelled buttons or pull-down menus in the left hand navigation window. The resulting Jmol display can also be controlled by a pull down menu produced by a right-mouse click in the right hand viewing window. ^(b)All calculations at the B3LYP/6-31G(d) level unless otherwise indicated. Energies are relative and are corrected for thermal and entropic terms. ^(c) Molecular orbital contoured at 0.015 a.u. ^(d)UV-Vis spectrum computed at the TD-DFT/B3LYP/6-31G(d)/SCRF(solvent=benzene) level and convoluted with a peak width of 0.14eV at half height using the program GaussView V4. The ²⁹Si NMR was computed at the GIAO level with SCRF(solvent=benzene) correction, 6-311+G(2df) basis on Si atoms, and 6-31G(d) basis on C and H atoms. ^(e)ρ(r)/η(r) isosurfaces, computed for reduced model comprising the Si framework only with methyl groups as substituents and 6-311G(d) basis and using the programs TopMod and DGrid 4.5. ^(f)Digital OAI-PMH compliant repository identifier for the primary calculation data (resolved as e.g. https://doi.org/10.14469/ch/2304). For details of the digital repository and the content, see DOI: 10.1021/ci7004737 ^(g)Centroids of ELF synaptic basins, the label indicating the integation of ρ(r) bounded by the basin, in units of electrons and computed using all the occupied MOs for compound 3c. For background information on the ELF method, see Ref. 31 in main article and DOI: 10.1002/anie.199201871 ^(h)Centroids of ELF synaptic basins, the label indicating the integation of ρ(r) bounded by the basin, in units of electrons and computed only for the HOMO to HOMO-3 for compound 3c. ⁽ⁱ⁾ELF isosurface computed using all the occupied MOs, contoured at a value of 0.755, and showing the start of the bifurcation into disynaptic basins in the central region. ^(j)ELF isosurface computed only for the HOMO, HOMO-2 and HOMO-3, revealing a torus link topology across the Si₄ central ring. ^(k)ρ(r) isosurface, at a value of 0.078 au, indicating critical point along Si(3)-Si(2) bond. For background information on the AIM technique, see Ref. 30 in main article. ^(l)ρ(r) isosurface, at a value of 0.073 au, indicating critical point along Si(3)-Si(1) bond. ^(m)For the isodesmic reaction 3b + disilane (Si₂H₆) → 4 + disilene (Si₂H₄).