Octahedral molybdenum iodide clusters with pyrazole or pyrazolate ligands

Due to the combination of useful physicochemical properties (luminescence, X-ray contrast, etc.), octahedral molybdenum halide cluster complexes [Mo6X8L6]n have been the subject of active investigation during the last decades. The most common methods for synthesizing new compounds with organic ligands involve the use of silver salts of organic acids or the substitution of terminal methylate ligands. However, these methods often necessitate the use of special conditions, such as an inert atmosphere, absolute solvents, and silver salts, which can be costly. In contrast, aqua-hydroxo complexes formed by hydrolysis of many complexes are considered final unreactive products, despite the tendency for them to form. This work proposes a simple and affordable method for the preparation of hexaaqua and hexahydroxo iodide clusters of molybdenum from [Mo6I14]2- in a single step. Furthermore, the possibility of using such compounds as starting complexes for the synthesis of clusters with organic ligands such as pyrazole is discussed. The paper presents synthetic approaches, detailed characterization both in solid and in solution, and a study of the reactivity and luminescence properties of the obtained compounds. Hexaaqua or hexahydroxo molybdenum iodide cluster complexes obtained in one step were shown to be accessible complexes for synthesis of clusters with pyrazole or pyrazolate ligands.