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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author Jana Pisk
Marko Dunatov
Martina Stojić
Nenad Judaš
Ivica Đilović
Marta Razum
Luka Pavić
author_facet Jana Pisk
Marko Dunatov
Martina Stojić
Nenad Judaš
Ivica Đilović
Marta Razum
Luka Pavić
author_sort Jana Pisk
collection DOAJ
description 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.
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spelling doaj-art-43eda99df2e5480198ad5555c7b643162025-08-20T02:47:13ZengMDPI AGMolecules1420-30492024-12-013018210.3390/molecules30010082Electrical Properties of Cu-Based Coordination Complexes: Insights from In Situ Impedance SpectroscopyJana Pisk0Marko Dunatov1Martina Stojić2Nenad Judaš3Ivica Đilović4Marta Razum5Luka Pavić6Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, CroatiaRuđer Bošković Institute, Bijenička Cesta 54, 10000 Zagreb, CroatiaDepartment of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, CroatiaDepartment of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, CroatiaDepartment of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000 Zagreb, CroatiaRuđer Bošković Institute, Bijenička Cesta 54, 10000 Zagreb, CroatiaRuđer Bošković Institute, Bijenička Cesta 54, 10000 Zagreb, CroatiaThis 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.https://www.mdpi.com/1420-3049/30/1/82copper complexes(thio)carbohydrazonesaroylhydrazonesimpedance spectroscopyelectrical properties
spellingShingle Jana Pisk
Marko Dunatov
Martina Stojić
Nenad Judaš
Ivica Đilović
Marta Razum
Luka Pavić
Electrical Properties of Cu-Based Coordination Complexes: Insights from In Situ Impedance Spectroscopy
Molecules
copper complexes
(thio)carbohydrazones
aroylhydrazones
impedance spectroscopy
electrical properties
title Electrical Properties of Cu-Based Coordination Complexes: Insights from In Situ Impedance Spectroscopy
title_full Electrical Properties of Cu-Based Coordination Complexes: Insights from In Situ Impedance Spectroscopy
title_fullStr Electrical Properties of Cu-Based Coordination Complexes: Insights from In Situ Impedance Spectroscopy
title_full_unstemmed Electrical Properties of Cu-Based Coordination Complexes: Insights from In Situ Impedance Spectroscopy
title_short Electrical Properties of Cu-Based Coordination Complexes: Insights from In Situ Impedance Spectroscopy
title_sort electrical properties of cu based coordination complexes insights from in situ impedance spectroscopy
topic copper complexes
(thio)carbohydrazones
aroylhydrazones
impedance spectroscopy
electrical properties
url https://www.mdpi.com/1420-3049/30/1/82
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