We discover MnVI -nanoparticles (NPs) bearing functional groups, high oxidation state, strong electron affinity, unique redox and paramagnetic nature, which opens up a new avenue to catalysis, magnetism and material application. However, its synthesis is challenging and remains unexplored because of associated serious difficulties. A simple benign synthetic strategy is devised to fabricate the high-valent NPs using mild reducing agent bromide, which transformed MnVII to valuable MnVI -species. The EELS-imaging of individual elements, ESI-MS, XPS and other techniques established its composition as Br(Me3 SiO)MnVI O2. It revealed significantly improved magnetic moment (SQUID) with isotropic hyperfine splitting of six line spectrum (EPR). The high-oxidation state and incorporated-ligands of the metals present on the active surface of the NPs led to development of a general catalytic process for oxidative heterodifunctionalisation to C-C triple bond towards formation of a new O-C/N-C/S-C and C-C coupling cum cyclisation to biologically important flavones and their aza- and marcapto-analogues, and valuable enaloxy synthons. © 2015, Nature Publishing Group. All rights reserved.