A building block strategy to access sulfur-functionalized polyoxometalate based systems using {Mo2S2O2} and {Mo3S4} as constitutional units, linkers or templates

Abstract

The present tutorial review reports on the synthetic approaches for the formation of "polyoxothiometalate" compounds with special emphasis on the unique reactivity of the preformed sulfur-containing cationic building blocks {Mo(2)O(2)S(2)}(2+) and {Mo(3)S(4)}(4+) toward polyoxometalate building blocks. Such simple chemical systems, based on chemical and structural complementarities between ionic reactive moieties have led to the synthesis of a series of relevant clusters with unrivalled large nuclearity structural arrangements, such as loops, triangles, squares and boxes. Specific reaction parameters and considerations will be pointed out showing that a deliberate pure inorganic supramolecular chemistry based on weak interactions, flexibility and dynamic is possible with polyoxometalates.

Crystal structure of Ir(III) complexes with 1,10-phenanthroline: K[Ir(phen)Cl4]·H2O and (Me4N)[Ir(phen)Cl4]

“…The complex [Ir(phen)Cl 4 ]cation can be a source of the {Ir(phen)} 3+ moiety for the incorporation into the structures of different polyoxometalates (polynuclear metal oxide complexes), which are now a key line in the development of modern inorganic chemistry [34,35]. The attention to the complexes with precious metals is special due to their activity in catalytic processes and, in particular, in the process of photocatalytic water cleavage [36,37].…”

Synthesis, Structure, and Tungsten NMR Characterization of {SbW9O33}9–{Mo2O2S2}2+ Sandwich‐Like Polyoxothiometalates

“…[10] The X-ray diffraction analysis revealed a sandwich-like cluster (Figure 1, a) consisting of two equivalent {SbW 9 O 33 } subunits linked by three equiva- [a] 0.0461 0.0969 R w (F 2 ) [b] 0.1361 0.2446 GOF 1.181 1.019 junction. In addition, a potassium ion is located within the sandwich-like arrangement and interacts with four terminal oxygen atoms belonging to the two {SbW 9 The three {Mo 2 O 2 S 2 } units lie parallel, forming a close, compact arrangement characterized by short S-S separations [S···S 3.563(9) Å] typical of van der Waals contacts.…”

“…[10] Solution studies combined with structural characterizations in the solid state showed that weak electrostatic interactions involving alkali cations govern the self-assembly process. [12] B-α-Na 9 6 ] 2+ in a ratio of 2:3 in aqueous solution at pH 4. The initial aim of this work was to extend this series of compounds to the antimony analogues constructed from the B-α-[SbW 9 O 33 ] 9trivacant anion.…”

“…The functionalization of POMs can be achieved through different and specific strategies depending upon the nature of the targeted property. [9] Coordination largely occurs at the equatorial and axial sites of the two equivalent Mo atoms predisposed to highly predictable self-assembly processes. An efficient strategy for obtaining polyoxothiometalates has been developed by Sécheresse and co-workers, who used the namely [(SbW 9 O 33 ) 2 (Mo 2 O 2 S 2 ) 3 ] 12 6 ] 2+ has been shown to be an efficient ditopic unit for linking highly negatively charged vacant heteropolyoxotungstates such as mono-, di-, tri-, tetra-, and superlacunary macrocyclic ions.…”

Acid–Base‐Triggered Structural Transformation of a Polyoxometalate Core Inside a Dodecahedrane‐like Silver Thiolate Shell

“…[21] However, the transformation of ap olyoxometalate core in silver(I) alkynyl or thiolate nanosized cage clusters has not been reported to date.B yrestriction inside an anosized cage,t he transformation of the polyoxometalate core may modulate the properties of the external silver(I) alkynyl or thiolate shell, and possibly lead to new POM/organosilver(I) functional materials. [21] However, the transformation of ap olyoxometalate core in silver(I) alkynyl or thiolate nanosized cage clusters has not been reported to date.B yrestriction inside an anosized cage,t he transformation of the polyoxometalate core may modulate the properties of the external silver(I) alkynyl or thiolate shell, and possibly lead to new POM/organosilver(I) functional materials.…”