{Mo2O2X2}2+ (X = O, S), a magic building block for the design of wheel shaped metalates

Abstract

The self-condensation of the [Mo 2 O 2 E 2 ] 2+ precursors is at the origin of a family of discrete cyclic species. The condensation can be performed in the presence or not of guest species. With E = O, the resulting cycles delimit an anionic open cavity, which can be filled by neutral polar molecules such as aquo ligands, or by alkaline cations. With E = S, the resulting cycles delimit a cationic cavity, which can be filled with neutral molecules, or anions like halides or more sophisticated groups like caboxylates. The flexibility of the rings is at the origin of striking host-guest properties: the symmetry and the nuclearity of the inorganic backbone are directed by the size and shape of the encapsulated guest. The metal coordination versatility confers to the ring unusual dynamic properties. In the solid state, molecular rings arrange in striking 3-D networks in which alkaline cations organize in pillars or layers decorated with anionic rings. The control of the partial occupancy of the cationic pillars permits to synthesize very good ionic conductors. To cite this article: F.

Screening of biological properties of MoV2O2S2- and MoV2O4-based coordination complexes: Investigation of antibacterial, antifungal, antioxidative and antitumoral activities versus growing of Spirulina platensis biomass

“…When used as building blocks in supramolecular polyoxometalate assemblies, the [Mo2O2S2] 2+ core is usually considered much more labile than its oxo analogue [Mo2O4] 2+ . [25,40] The same phenomenon is expected in coordination complexes. However, the spectrum of Na-Mo2O4-EDTA shows something that looks like two very broad signals corresponding to the 12 protons of coordinated EDTA ligand, in contrast to its sulfido bridged analogue.…”

“…[39] The resulting red-orange solution then reacts with the ligand, which is introduced in excess in order to avoid the formation of cyclic compounds, well-known with this cluster. [26,28,33,[39][40][41] Mo2O2S2-based complexes are obtained preferably as K + salts, while the oxo homologues are more easily prepared in the form of Na + salts. The corresponding synthetic procedures are detailed in the experimental section given in the Supporting Information (SI).…”

Structure, Formation, and Dynamics of Mo12 and Mo16 Oxothiomolybdenum Rings Containing Terephtalate Derivatives

“…[19,20] This system was shown to be fruitful for developing extended cyclic inorganic clusters, differing in their nuclearity and shape by the nature of the encapsulated substrate, being either mono-or polyphosphates, [21][22][23] metalates, [24][25][26] or polycarboxylates. [27][28][29] The flexible and adaptable cyclic oxothiomolybdenum rings exhibiting an open inner available cavity, display attractive properties for bioin- 16 …”

Syntheses, characterizations and properties of [Mo2O2S2]-based oxothiomolybdenum wheels incorporating bisphosphonate ligands

“…Driven by these results, the aim of the present study was to compare the electrocatalytic activity of two analogous compounds, one based on the [Mo 2 O 2 S 2 ] building-unit and the other on the [Mo 2 O 4 ] fragment in order to demonstrate the role of the bridging sulfides in the HER process. To date, a large family of cyclic polyoxomolybdates built from the connections of the [Mo 2 O 4 ] 2+ cations by bisphosphonate ligands (BPs) has been isolated, [27][28][29][30][31][32][33][34] units via hydroxo bridges. Such a spontaneous cyclization process, mainly entropically driven, has allowed the development of relevant host-guest chemistry using various organic ligands as template agents.…”