Gurdal, YelizIannuzzi, Marcella2025-01-062025-01-0620201439-42351439-764110.1002/cphc.2020006002-s2.0-85097007349https://doi.org/10.1002/cphc.202000600https://hdl.handle.net/20.500.14669/1726Understanding water reduction towards H-2 generation is crucial to overcome today's renewable energy obstacles. Previous studies have shown the superior H-2 production performances of Cobalt based penta-pyridyl (CoaPPy) and tetra-pyridyl (CoaTPy) complexes in solution. We investigate H-2 production cycles of CoaPPy and CoaTPy complexes immersed in water solution by means of Ab-initio Molecular Dynamics and Density Functional Theory. We monitor dynamic properties of the systems, solvent response and structural changes occurring in the catalysts, by simulating all intermediate steps of the H-2 production cycle. Reduction free energies and reorganization energies are calculated. Our results show that, following the first electron injection, H-2 production proceeds with the singlet spin state. Following the first electron insertion, we observe a significant rearrangement of the hydrogen bonding network in the first solvation shell. The cobalt center turns out to be more accessible for the surrounding water molecules in the case of CoaTPy at all the intermediate steps, which explains its higher catalytic performance over CoaPPy. Following the first reduction reaction, a larger gain in reduction free energy is estimated for CoaTPy with respect to CoaPPy, with a difference of 0.14 eV, in line with the experiments. For the second reduction, instead, CoaPPy shows more negative reduction potential, by 0.41 eV.eninfo:eu-repo/semantics/closedAccessab-initio molecular dynamicscobalt-bipyridine-pyridine based catalystsdensity functional theoryreduction free energywater reductionArticle27002432955784Q2269221WOS:000591684400001Q2