Chemical Diversity of Mo5S5 Clusters with Pyrazole: Synthesis, Redox and UV-vis-NIR Absorption Properties.

The chemistry of transition metal clusters has been intensively developed in the last decades, leading to the preparation of a number of compounds with promising and practically useful properties. In this context, the present work demonstrates the preparation and study of the reactivity, i.e., the possibility of varying the ligand environment, of new square pyramidal molybdenum chalcogenide clusters [{Mo5(µ3-S)i4(µ4-S)i(µ-pz)i4}(pzH)t5]1+/2+ (pzH = pyrazole, i = inner, t = terminal). The one-step synthesis starting from the octahedral Mo6Br12 cluster as well as the substitution of the apical pyrazole ligand or the selective bromination of the inner pyrazolate ligands were demonstrated. All the obtained compounds were characterized in detail using a series of physicochemical methods both in solid state (X-ray diffraction analysis, etc.) and in solution (nuclear magnetic resonance spectroscopy, mass spectrometry, etc.). In this work, redox properties and absorption in the ultraviolet-visible and near-infrared region of the obtained compounds were studied.

Unusual Square Pyramidal Chalcogenide Mo5 Cluster with Bridging Pyrazolate-Ligands.

The family of chalcogenide molybdenum clusters is well presented in the literature by a series of compounds of nuclearity ranging from binuclear to multinuclear articulating octahedral fragments. Clusters actively studied in the last decades were shown to be promising as components of superconducting, magnetic, and catalytic systems. Here, we report the synthesis and detailed characterization of new and unusual representatives of chalcogenide clusters: square pyramidal complexes [{Mo5(µ3-Se)i4(µ4-Se)i(µ-pz)i4}(pzH)t5]1+/2+ (pzH = pyrazole, i = inner, t = terminal). Individually obtained oxidized (2+) and reduced (1+) forms have very close geometry (proven by single-crystal X-ray diffraction analysis) and are able to reversibly transform into each other, which was confirmed by cyclic voltammetry. Comprehensive characterization of the complexes, both in solid and in solution, confirms the different charge state of molybdenum in clusters (XPS), magnetic properties (EPR), and so on. DFT calculations complement the diverse study of new complexes, expanding the chemistry of molybdenum chalcogenide clusters.

Aluminothermic Synthesis of Dispersed Electrides Based on Mayenite: XRD and EPR Study.

The evolution of the structure and the phase composition of a dispersed mayenite at its interaction with metallic aluminum was studied in a temperature range from 900 to 1400 °C in both argon and air atmospheres. The aluminum loading was varied from 0 to 50 wt%. It was found that the addition of aluminum significantly affects the stability of the mayenite and other calcium aluminate phases within the studied temperature range. The formation of the electride state registered by the appearance of a characteristic electron paramagnetic resonance (EPR) signal from F+-like centers (g~1.994) in an argon atmosphere was shown to take place already at 1150 °C due to an aluminothermic reduction of this material. The super-narrow (Hp-p < 0.5 G) EPR spectra from F+-like centers, which were recently observed for the core−shell structures of the C12A7@C type only, were registered for mayenite for the first time. The results obtained in the present study testify firstly towards the possibility of significantly diminishing the temperatures required for the formation of the electride state in such systems and secondly towards the ability to stabilize the size of small electride nanoparticles within the synthesized calcium aluminate matrix.