The challenge motivating this paper is to induce, by chemical substitution, a silylyne, SiR, or a congeneric carbyne, CR, to adopt the high-spin quartet rather than the low-spin doublet as its ground state. The difficulty is seen in the preference for the doublet of the parent SiH (doublet-quartet energy difference,similar to 39 kcal/mol, favoring the doublet) or CH (similar to 17 kcal/mol). Strategies for having high-spin ground state parallel those for silylenes and carbenes: greater electropositivity (sigma-donation) and pi-acceptance of the single substituent favor the high-spin state. The electronegativity trend can be understood from an ions in molecules way of thinking already present in the literature in the works of Boldyrev and Simons, and of Mavridis and Harrison; i.e., the quartet ground state spin of some CR/SiR species is largely determined by the ground state spin of C-/Sr-. In this study, we provide a diabatization analysis that solidly confirms the ions in molecules picture and explains the difference in the equilibrium internuclear distances for the two spin states. In general, electronegativity dominates the ordering of spin states. pi-Acceptors also help to lower the quartet state energy of the many carbynes (silylynes) examined, whose range of doublet-quartet differences calculated is impressive, 120 (100) kcal/mol. The qualitative understanding gained leads to the prediction of some quartet-ground state carbynes (CMgH, CAlH2, CZnH, CSiH3, CSiF3, etc.) and a smaller number of silylynes (SiMgH, SiMgF, SiBeH, etc.). A beginning is made on the energetics of approach geometries of the fragments in the highly exoergic dimerization of CH to acetylene; it should proceed for the ground state doublet CH through C-2h-like trajectories, with no activation energy.