We have demonstrated reversibly reducing metal-ion crosslinkages in polymer systems, by harnessing light, creating a dynamic and reversible bond. The reduction induces chemical and physical changes in the polymer materials. Some variations provide a polymer composition comprising: a polymer matrix containing one or more ionic species; one or more photosensitizers; and one or more metal ions capable of reversibly changing from a first oxidation state to a second oxidation state when in the presence of the photosensitizers and light. Some embodiments employ urethane-based ionomers capable of changing their crosslinked state under the influence of a change in counterion valance, using light or chemical reducing agents. This invention provides films, coatings, or objects that are reversible, re-mendable, self-healing, mechanically adjustable, and/or thermoplastic/thermoset-switchable.