Host–Guest Hybrid Redox Materials Self‐Assembled from Polyoxometalates and Single‐Walled Carbon Nanotubes

The development of next-generation molecular-electronic, electrocatalytic, and energy-storage systems depends on the availability of robust materials in which molecular charge-storage sites and conductive hosts are in intimate contact. It is shown here that electron transfer from single-walled carbon nanotubes (SWNTs) to polyoxometalate (POM) clusters results in the spontaneous formation of host-guest POM@SWNT redox-active hybrid materials. The SWNTs can conduct charge to and from the encapsulated guest molecules, allowing electrical access to >90% of the encapsulated redox species. Furthermore, the SWNT hosts provide a physical barrier, protecting the POMs from chemical degradation during charging/discharging and facilitating efficient electron transfer throughout the composite, even in electrolytes that usually destroy POMs.