Composite nano- and micromaterials and methods of making and using same. The composite materials comprise crystalline materials (e.g., binary and ternary vanadium oxides) in an amorphous or crystalline material (e.g., oxide, sulfide, and selenide materials). The materials can be made using sol-gel processes. The composite materials can be present as a film on a substrate. The films can be formed using preformed composite materials or the composite material can be formed in situ in the film forming process. For example, films of the materials can be used in fenestration units, such as insulating glass units deployed within windows.