Electrical Properties of Cu-Based Coordination Complexes: Insights from In Situ Impedance Spectroscopy

This study examines the influence of ligand design on the structural, optical, and electrical properties of copper-based coordination complexes. Ligands H<sub>2</sub>L<sup>1</sup> and H<sub>2</sub>L<sup>2</sup> were synthesized via the reaction of 5-ni...

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Main Authors: Jana Pisk, Marko Dunatov, Martina Stojić, Nenad Judaš, Ivica Đilović, Marta Razum, Luka Pavić
Format: Article
Language:English
Published: MDPI AG 2024-12-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/30/1/82
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Summary:This study examines the influence of ligand design on the structural, optical, and electrical properties of copper-based coordination complexes. Ligands H<sub>2</sub>L<sup>1</sup> and H<sub>2</sub>L<sup>2</sup> were synthesized via the reaction of 5-nitrosalicylaldehyde with 2-hydroxy- or 4-hydroxybenzhydrazide. H<sub>4</sub>L<sup>3</sup> was obtained from the reaction of carbohydrazide and salicylaldehyde, while H<sub>4</sub>L<sup>4</sup> was prepared by condensing 4-methoxysalicylaldehyde with thiocarbohydrazide. The research focuses on two key design elements: (1) the effect of hydroxyl group positioning on the aroyl ring in hydrazide ligands (H<sub>2</sub>L<sup>1</sup> vs. H<sub>2</sub>L<sup>2</sup>) and (2) the impact of carbonyl versus thiocarbonyl groups and aldehyde substituents in hydrazone ligands (H<sub>4</sub>L<sup>3</sup> vs. H<sub>4</sub>L<sup>4</sup>). The resulting complexes, [Cu<sub>2</sub>(L<sup>1</sup>)<sub>2</sub>], [Cu<sub>2</sub>(L<sup>2</sup>)<sub>2</sub>(MeOH)<sub>3</sub>], [Cu<sub>2</sub>(L<sup>3</sup>)(H<sub>2</sub>O)<sub>2</sub>], and [Cu<sub>2</sub>(L<sup>4</sup>)(H<sub>2</sub>O)<sub>2</sub>], were synthesized and characterized using attenuated total reflectance infrared (IR-ATR) spectroscopy, thermogravimetric analysis (TG), and UV-Vis diffuse reflectance spectroscopy. Their electrical properties were investigated using solid-state impedance spectroscopy (IS). The crystal and molecular structure of the complex [Cu<sub>2</sub>(L<sup>2</sup>)<sub>2</sub>(MeOH)<sub>3</sub>]∙MeOH was determined by single-crystal X-ray diffraction (SCXRD). This study underscores the pivotal role of ligand modifications in modulating the functional properties of coordination complexes, offering valuable insights for the advancement of materials chemistry.
ISSN:1420-3049