Methods are disclosed of making linear and cross-linked, HMW (high molecular weight) polysilanes and polygermanes, polyperhydrosilanes and polyperhydrogermanes, functional liquids containing the same, and methods of using the liquids in a range of desirable applications. The silane and germane polymers are generally composed of chains of Si and / or Ge substituted with R′ substituents, where each instance of R′ is, for example, independently hydrogen, halogen, alkenyl, alkynyl, hydrocarbyl, aromatic hydrocarbyl, heterocyclic aromatic hydrocarbyl, SiR″3, GeR″3, PR″2, OR″, NR″2, or SR″; where each instance of R″ is independently hydrogen or hydrocarbyl. The cross-linked polymers can be synthesized by dehalogenative coupling or dehydrocoupling. The linear polymers can be synthesized by ring-opening polymerization. The polymers can be further modified by halogenation and / or reaction with the source of hydride to furnish perhydrosilane and perhydrogermane polymers, which are used in liquid ink formulations. The synthesis allows for tuning of the liquid properties (e.g., viscosity, volatility, and surface tension). The liquids can be used for deposition of films and bodies by spincoating, inkjetting, dropcasting, etc., with or without the use of UV irradiation. The deposited films can be converted into amorphous and polycrystalline silicon or germanium, and silicon or germanium oxide or nitride by curing at 400-600 DEG C. and (optionally) laser- or heat-induced crystallization (and / or dopant activation, when dopant is present).