Advances in gigantic polyoxomolybdate chemistry

Since 1996 when Muller et al. determined the first giant Molybdenum Blue (MB) wheel {Mo154} and revealed the 200-year-old mystery, many hundreds of compounds of this type and analogous giant polyoxomolybdates have been discovered. These multifunctional and highly complex molecular nano-objects of reduced molybdenum oxide, reaching to the size of proteins, have potential applications in materials science, catalysis, electronic devices and even as biosensors. This family of molecules displays exquisite structures, and even opens the way for adaptive and autocatalytic chemistry. Muller and a few other groups published a number of exceptional reviews on the topic of giant polyoxomolybdates. This chapter presents a detailed summary of recent advances including new synthetic methods, characterization, supramolecular chemistry and applications, focusing on recent work on lanthanide-substituted and amino-acid/peptide functionalized MB wheels, confined reaction in the Keplerate {Mo132} ball and the new discovery of Molybdenum Reds.