Self-assembly of polyoxotungstate with tetrarhodium-oxo core: synthesis, structure and 183W NMR studies

Abstract

A sandwich-type rhodium polyoxotungstate with unprecedented tetrarhodium-oxo core Na(12)[(Rh(4)(μ(3)-O)(2)(H(2)O)(2))(H(2)W(9)O(33))(2)]·38H(2)O (1) was obtained by hydrothermal reaction of rhodium(II) acetate and sodium tungstate; crystal structure was determined by X-ray diffractometry and was confirmed by (183)W NMR data; 1 is active in electrocatalytic water oxidation.

Polyoxoniobates and Polyoxotantalates as Ligands—Revisited

“…The current in the presence of the platinum niobate is several times higher than for the blank solution. This electrochemical behavior is similar to the reported for the nonatungstate complex with a tetrarhodium-oxo core [51]. , which led them to the wrong conclusion about the composition of the product.…”

High‐field95Mo and183W static and MAS NMR study of polyoxometalates

“…Very often POMs can be grown as single crystals, allowing their structure determination from single‐crystal X‐ray diffraction data. Furthermore, NMR spectroscopy has been shown to be a technique of choice to study their structure and stability in solution, and liquid‐state NMR experiments ( 17 O, 31 P, 51 V, 95 Mo or 183 W) are routinely performed nowadays . For example, 183 W NMR, including J ‐based experiments, was proven useful to verify structures, to solve some local structural ambiguities and assign all signals .…”

Crystallographic analysis of a series of inorganic compounds

“…Since the structure is cubic, the distances between the polyanions in all three identical projections are specified by interplanar distances between the close-packed cation {420} planes and their symmetryrelated analogues. The highly symmetric configuration of this polyanion is retained also in the case of an essentially different cation composition, namely, in the mineral aspedamite (Fe 3+ ,Fe 2+ ) 3 152 is an example of coherent assembly from more complex fragments; the molecular symmetry of this polyanion includes only a centre of inversion (Table 14, Fig. 27).…”

“…148,152 The distinguishing feature of the synthesis of crystalline phases of these compounds is the energy gain due to the formation of large fragments with high local symmetry, both chemical interactions and the three-dimensional ordering being involved in this process. Therefore, such processes are characterized as the first crystallization step.…”