From structure to function: tunable electrical and catalytic properties in rare Mo(vi)-thiophene-2-carboxylic acid hydrazone complexes obtained mechanochemically

TL;DR

This paper reports the green synthesis of molybdenum complexes with unique electrical and catalytic properties using a thiophene-based ligand.

Contribution

The study introduces rare Mo-based materials with tunable electrical and catalytic properties synthesized via a green mechanochemical route.

Findings

The Mo complex [MoO2(L)(MeOH)] efficiently catalyzes benzyl alcohol oxidation under mild conditions.

The complexes exhibit semiconducting behavior with DC conductivities of ~10−12 (Ω cm)−1 and activation energies of ~60–63 kJ mol−1.

Dielectric measurements show frequency-dependent polarization dominated by Maxwell–Wagner effects with dielectric constants of ~11–13.

Abstract

This study focuses on the synthesis of molybdenum complexes coordinated with a thiophene-2-carboxylic acid hydrazone-type ligand (H2L), obtained via mechanochemical reaction condensation of 2-hydroxybenzaldehyde with thiophene-2-carboxylic acid hydrazide. The Mo complexes were prepared via a green mechanochemical route, [MoO2(L)(MeOH)] and [MoO2(L)]n, while the complex [MoO2(L)(H2O)] was obtained by classic solution-based synthetic pathway. All obtained compounds were characterized using attenuated total reflectance infrared spectroscopy (IR-ATR), elemental analysis (EA), and thermogravimetric analysis (TGA). The crystal and molecular structures of the ligand H2L and the complexes [MoO2(L)(MeOH)] and [MoO2(L)(H2O)]·(CH3)2CO were elucidated by means of single-crystal X-ray diffraction (SCXRD) analysis. Catalytic studies revealed that complex [MoO2(L)(MeOH)] efficiently promoted the oxidation of benzyl alcohol under mild conditions, employing hydrogen peroxide as a green oxidant. Solid-state impedance spectroscopy (ss-IS) confirmed the semiconducting behavior, with DC conductivities of ∼10−12 (Ω cm)−1 and activation energies of ∼60–63 kJ mol−1, consistent with electronic transport. Dielectric insights revealed frequency-dependent polarization processes dominated by Maxwell–Wagner interfacial effects, with dielectric constants of ∼11–13. The novelty of this work lies in the green development of rare Mo-based materials that uniquely combine structural, electrical, and catalytic features. Importantly, this study establishes correlations between these properties, representing, to the best of our knowledge, one of the first systematic investigations of molybdenum coordination complexes incorporating thiophene–carbohydrazide ligands.

This study focuses on the synthesis of Mo complexes coordinated with a thiophene-2-carboxylic acid hydrazone-type ligand (H2L), obtained via mechanochemical reaction condensation of 2-hydroxybenzaldehyde with thiophene-2-carboxylic acid hydrazide.

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