Abstract
This article describes the structural authentication of a unique triply bridged [1](ClO4)2 and monomeric [2]ClO4/[3]ClO4. Electrochemical HER on a carbon cloth support demonstrated the superior performance of [1](ClO4)2 with high TON (>105) and its long-term stability. The primary kinetic isotope effect of [1](ClO4)2 revealed the involvement of PCET in the rate-determining step.
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