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Two new nickel dithiolate derivatives have been examined for their electrocatalytic activity for the hydrogen evolution reaction (HER) in attempts to clarify whether the overpotential for the HER can be tuned upon varying the ligand-centered reduction potential that triggers the HER by the catalysts. We demonstrate the validity of this approach to achieve desirable tunability in the overpotential for the HER.

Graphical abstract: A family of molecular nickel hydrogen evolution catalysts providing tunable overpotentials using ligand-centered proton-coupled electron transfer paths

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