Abstract

A discrete class of metal–oxygen clusters, Polyoxometalates (POMs) have received tremendous attention for their convenient shapes, sizes, compositions and structural diversities. Amongst their numerous advantages, one that stands out is their ability to be modified at molecular level, giving rise to second, third and even fourth generation materials. In this regard, Transition Metal Substituted Polyoxometalates (TMSPOMs), a subclass of POMs, are extremely relevant even today. Amongst, Mn substituted POMs (Mn-POMs) visibly attract significant attention due to variable oxidation states, redox and magnetic properties. Mn-POMs, themselves comprise an entire arena of inorganic building blocks with large assortments of morphologies, structural flexibility and functionality. Herein, we have compiled the different syntheses, strategies for modification, characterizations as well as diverse applications of Mn containing Keggin and Dawson POMs. We have also catalogued the available literature on the synthesis and applications of Mn-POMs, modified via functionalization as well as supporting. Our intension behind this review is to provide readers, in-depth insights, and a fundamental, representative and comprehensive overview of the work done so far in this emerging field, emphasizing on industrially viable catalytic systems. Thus, the article would appeal not only to POMs community but also to Crystallographers, electrochemists as well as physical chemists.

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