Synthesis, Crystal Structures, Hirshfeld Surface Analysis, Computational Investigations, Thermal Properties, and Electrochemical Analysis of Two New Cu(II) and Co(II) Coordination Polymers with the Ligand 5-Methyl-1-(pyridine-4-yl-methyl)-1H-1,2,3-triazole-4-carboxylate.
Markus Bergedahl, Pilar Narea, Jaime Llanos, Ruth Pulido, Nelson Naveas, Pilar Amo-Ochoa, Félix Zamora, Gerzón E Delgado, Felipe M Galleguillos Madrid, Yasna León, Iván Brito
Author Information
Markus Bergedahl: Departamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta 1240000, Chile.
Pilar Narea: Departamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta 1240000, Chile.
Jaime Llanos: Departamento de Química, Facultad de Ciencias, Universidad Católica del Norte, Avda. Angamos 0610, Antofagasta 1270709, Chile. ORCID
Ruth Pulido: Departamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta 1240000, Chile.
Nelson Naveas: Instituto Universitario de Ciencia de Materiales "Nicolás Cabrera" (INC), Universidad Autónoma de Madrid, Campus de Cantoblanco, 28049 Madrid, Spain. ORCID
Pilar Amo-Ochoa: Departamento de Química Inorgánica, Universidad Autónoma de Madrid, 28049 Madrid, Spain. ORCID
Félix Zamora: Departamento de Química Inorgánica, Universidad Autónoma de Madrid, 28049 Madrid, Spain. ORCID
Gerzón E Delgado: Laboratorio de Cristalografía, Departamento de Química, Facultad de Ciencias, Universidad de Los Andes, Mérida 5101, Venezuela. ORCID
Felipe M Galleguillos Madrid: Centro de Desarrollo Energético de Antofagasta, Universidad de Antofagasta, Av. Universidad de Antofagasta 02800, Antofagasta 1240000, Chile. ORCID
Yasna León: Departamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta 1240000, Chile.
Iván Brito: Departamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta 1240000, Chile. ORCID
Two new Cu(II) (CP1) and Co(II) (CP2) coordination polymers (CPs) with the triazole ligand 5-methyl-1-(pyridin-4-yl-methyl)-1H-1,2,3-triazole-4-carboxylate (L1) have been synthesized and structurally characterized by SCXRD (Single Crystal X-Ray Difraccion), PXRD (Power X-Ray Difracction), FT-IR (Fourier Transform Infrared), TG (Theermo Gravimetric), and electrochemical techniques. Both CPs were obtained at the water/n-butanol interface by reacting nitrate salts of each metal with the NaL1 ligand. SCXRD analysis revealed that CP1 (Coordination Polymer 1) and CP2 (Coordination Polymer 2) crystallize in the monoclinic space groups C2/c (No. 15) and P2/n (No. 14), respectively, forming 1D zigzag chain structures, which further lead to a 2D supramolecular network through O-H⋯O and C-H⋯O hydrogen bond interactions, respectively. In CP1, the supramolecular structure is assembled by hydrogen bonds involving water molecules. In contrast, CP2 forms its supramolecular network mainly through hydrogen bonds between adjacent triazole ligand molecules. Hirshfeld surface analysis revealed that the most significant contributions to the crystal packing come from H⋯O/O⋯H, H⋯H, H⋯N/N⋯H, and H⋯C/C⋯H interactions. In addition, FT-IR provided information on the functional groups involved in the coordination, while the decomposition patterns of both CPs were evaluated by TGA. Electrochemical studies conducted in a saline environment showed that CP1 exhibits superior hydrogen evolution reaction (HER) kinetics compared to CP2, as evidenced by a higher exchange current density and a lower Tafel slope. Density functional theory calculations and experimental bandgap measurements provided a deeper understanding of the electronic properties influencing the electrochemical behavior. The results highlight the potential of CP1 as an efficient catalyst for HER under saline conditions.
