Electronic Structure Studies on the Whole Keplerate Family: Predicting New Members

Abstract

The present paper presents a comprehensive study of the electronic structure of nano-scale molecular oxide capsules of the type [{M O 2 (μ-O) 2 } linker moiety produces negligible effects on its stability which is evidence of a strong ionic component in these bonds. The existence of hitherto unknown species, namely W 132 with both bridging alternatives is discussed and put into context with our findings.

Metal–metal bonds in polyoxometalate chemistry

“…92 The highest occupied molecular orbitals in the later polyanion are elegantly delocalised between the pairing Mo V centres of each linking unit. 93 Müller's {Mo132} and its derivatives have been overwhelmingly covered in many excellent reviews ranging from molecular magnetism, 94 homogeneous catalysis, 95 to supramolecular chemistry. 96 The linking nature of the {Mo2O8} moieties is also noticed in Kabanos' [(Mo V 2O4)3(μ2-O)3(μ2-SO3)3(μ6-SO3)] 8− polyanion which in the solid-state dimerises with the help of a single sodium cation, forming [Na{(Mo V 2O4)3(μ2-O)3(μ2-SO3)3(μ6-SO3)}2] 15− (Figure 4.c).…”

A redox-active inorganic crown ether based on a polyoxometalate capsule

“…Because of the large size of the system, density of states (DOS) plots, which are more typical of bands in solids, were utilized to visualize the electronic structure. 40 In the total density of states (TDOS) (Fig. S7 † ), the deepest bands around −25 eV comprise 2s oxygen electrons and some contribution of p metal orbitals, and the wide band from −15 eV till below the HOMO area known as the oxo-band corresponds to 2p oxygen electrons, which mix with empty d metal orbitals.…”

Selective Photocatalytic C–C Bond Cleavage of Lignin Models and Conversion to High-Value Chemical by Polyoxometalate Under a Mild Water-Based Environment

“…Furthermore, they are thermally and oxidatively stable compared to other organic or organometallic-based homogeneous catalysts, and the reduced POM during reaction can be easily re-oxidized by O 2 . Especially, for giant Keplerate-type POMs with a unique nanoporous structure and multiple reaction sites, their chemical properties and redox potential can be readily tuned by changing metal and ligand compositions, which would be advantageous to the study of redox potential relevance with chemical bond cleavage. − …”