Bis(aminothiolato)nickel nanosheet as a redox switch for conductivity and an electrocatalyst for the hydrogen evolution reaction

A π-conjugated coordination nanosheet comprising bis(aminothiolato)nickel (NiAT) moieties was synthesized by the reaction of Ni(acac)₂ with 1,3,5-triaminobenzene-2,4,6-trithiol at liquid-liquid and gas-liquid interfaces. The sheet thickness could be controlled down to a single layer (0.6 nm). Selected area electron diffraction and grazing incidence X-ray diffraction analyses indicated the formation of a flat crystalline sheet with a kagome lattice stacked in a staggered alignment. NiAT was reversibly interconverted to a bis(iminothiolato)nickel (NiIT) nanosheet by the chemical 2H⁺-2e^- reaction, which was accompanied by a drastic change in electrical conductivity from 3 × 10^-6 to 1 × 10^-1 S cm^-1. This change in conductivity was explained by the difference in band structures between NiAT and NiIT. NiAT acted as an efficient electrocatalyst for the hydrogen evolution reaction, showing strong acid durability and an onset overpotential of -0.15 V.