Inorganic siloxane ladder polymers with metal-aza/thio crown complexes, and methods of making and using such siloxane ladder polymers are disclosed. The polymers described herein may exhibit self-healing properties, a low dielectric constant, and a low refractive index. These siloxane ladder polymers are anchored to transparent, high-refractive index (RI) metal nanoparticles, such as ZrO2, via aza/thio crown macromolecules. The siloxane ladder polymers may be considered as “living polymer network” since the polymer active chain ends may further undergo anionic polymerization.