Electronic Effects Governing the Redox Properties of Polyoxometalates

Identifier:  TDX:2046

Handle: https://hdl.handle.net/20.500.11797/TDX2046

Authors:  Aparicio Sánchez, Pablo Arturo

Abstract:
The polyoxometallates (POMs) aggregates are inorganic compounds of transition metals and oxygen, usually in its highest oxidation state. This fact makes one of its main characteristics is its high oxidizing character. In addition to they contain a large number of metals, that can be easily reduced, resulting in new properties not observed in the same compounds without reducing. Our studies have been based mainly on quantum mechanical calculations (theory of density functional, DFT). Many experimental studies have been conducted over the past decades covering the issue of mono-reductions where these compounds gain an electron. In this thesis we have started from these results and we have extended the study to the reductions with two and three electrons in various systems of different size and composition. We focused mainly on the study of compounds called Keggin (12 metals) and Wells-Dawson (18 metals) polyoxoanions. Furthermore, derivatives of these compounds have also been studied, in particular the mono-substituted, wherein one of the metals is replaced by a different one.