Thermoplastic polyurethanes having an alternating sequence of hard and soft segments in which a nanostructured polyhedral oligosilsesquioxane diol is used as a chain extender to form a crystalline hard segment constituting SMPs. The polyurethanes are formed by reacting a polyol, a chain extender dihydroxyl-terminated polyhedral oligosilsesquioxane and a diisocyanate. The polyurethanes have multiple applications including for example, implants for human health care, drug delivery matrices, superabsorbant hydrogels, coatings, adhesives, temperature and moisture sensors, etc.