A new doubly carboxylato-bridged Co(ii) dinuclear complex, [Co(bdtbpza)(NCS)](2) (1), was obtained in a satisfactory yield by employing a 'scorpionate'-type precursor, bdtbpza {bis-(3,5-di-tert-butylpyrazol-1-yl)acetate}, and was then structurally characterized. Single-crystal X-ray diffraction analysis revealed that, in 1, each Co(ii) is penta-coordinated, leading to a distorted trigonal-bipyramidal geometry within the coordination environment of N3O2. Weak antiferromagnetic coupling within the Co(ii) ions in 1 was found based on the isotropic spin Hamiltonian H = -J(S-1S-2) for the S-i = 3/2 system. For evaluating the spin density distribution and the mechanism for the magnetic exchange coupling, DFT analysis was performed, with the calculated result agreeing the experimental magnetic data. A study into electrochemical H-2 evolution, involving cyclic voltammetry (CV), controlled potential electrolysis (CPE), and gas chromatographic (GC) analyses of the graphite electrode modified with the cobalt complex in a neutral aqueous solution revealed the high catalytic activity of the complex with a low overpotential toward H2O reduction. The faradaic efficiency of the catalyst was found to be 83.7% and the di-cobalt catalyst-modified electrode displayed quite an interesting H-2-evolution activity compared with that of bare electrodes. These results are encouraging for the future potential application of 1 in water splitting.

Magnetic study and DFT analysis of a doubly carboxylato-bridged Co(ii) derivative anchored with a ‘scorpionate’ precursor as a potential electrocatalyst for heterogeneous H2 evolution / Das, Kuheli; Beyene, Belete B.; Massera, Chiara; Garribba, Eugenio; El Fallah, M. S.; Frontera, Antonio; Hung, Chen-Hsiung; Datta, Amitabha. - In: DALTON TRANSACTIONS. - ISSN 1477-9226. - 53:22(2024), pp. 9358-9368. [10.1039/d4dt00807c]

Magnetic study and DFT analysis of a doubly carboxylato-bridged Co(ii) derivative anchored with a ‘scorpionate’ precursor as a potential electrocatalyst for heterogeneous H2 evolution

Garribba, Eugenio;
2024-01-01

Abstract

A new doubly carboxylato-bridged Co(ii) dinuclear complex, [Co(bdtbpza)(NCS)](2) (1), was obtained in a satisfactory yield by employing a 'scorpionate'-type precursor, bdtbpza {bis-(3,5-di-tert-butylpyrazol-1-yl)acetate}, and was then structurally characterized. Single-crystal X-ray diffraction analysis revealed that, in 1, each Co(ii) is penta-coordinated, leading to a distorted trigonal-bipyramidal geometry within the coordination environment of N3O2. Weak antiferromagnetic coupling within the Co(ii) ions in 1 was found based on the isotropic spin Hamiltonian H = -J(S-1S-2) for the S-i = 3/2 system. For evaluating the spin density distribution and the mechanism for the magnetic exchange coupling, DFT analysis was performed, with the calculated result agreeing the experimental magnetic data. A study into electrochemical H-2 evolution, involving cyclic voltammetry (CV), controlled potential electrolysis (CPE), and gas chromatographic (GC) analyses of the graphite electrode modified with the cobalt complex in a neutral aqueous solution revealed the high catalytic activity of the complex with a low overpotential toward H2O reduction. The faradaic efficiency of the catalyst was found to be 83.7% and the di-cobalt catalyst-modified electrode displayed quite an interesting H-2-evolution activity compared with that of bare electrodes. These results are encouraging for the future potential application of 1 in water splitting.
2024
Magnetic study and DFT analysis of a doubly carboxylato-bridged Co(ii) derivative anchored with a ‘scorpionate’ precursor as a potential electrocatalyst for heterogeneous H2 evolution / Das, Kuheli; Beyene, Belete B.; Massera, Chiara; Garribba, Eugenio; El Fallah, M. S.; Frontera, Antonio; Hung, Chen-Hsiung; Datta, Amitabha. - In: DALTON TRANSACTIONS. - ISSN 1477-9226. - 53:22(2024), pp. 9358-9368. [10.1039/d4dt00807c]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11388/348371
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