An "All-Terrain" Ligand Design Strategy: Phosphorus-Functionalized Nickel Thiosemicarbazones for Hydrogen Evolution in Organic and Aqueous Media
Abstract
We report the synthesis and characterization of a series of mononuclear nickel thiosemicarbazone complexes bearing phosphorus-functionalized phenyl groups designed to improve their solubility and tune their catalytic properties for hydrogen evolution. NiTSC-PO(OEt)₂ and NiTSC-PO(OH)₂, which carry diethyl phosphonate and phosphonic acid groups, respectively, at the para position of the ligand phenyl rings, were investigated in dimethylformamide using trifluoroacetic acid as the proton source. NiTSC-PO(OH)₂ exhibited notable catalytic activity in aqueous acetate buffer and its photocatalytic performance was further evaluated in combination with nitrogen-doped carbon dots as photosensitizers and a mixture of tris(2-carboxyethyl)phosphine/ascorbic acid as sacrificial electron donor. The two complexes display complementary performances: NiTSC-PO(OEt)2 is the more active electrocatalyst in organic medium, whereas NiTSC-PO(OH)2 operates in water and under photocatalytic conditions. Ligand functionalization thus influences catalytic activity through both solubility and electronic effects, showing that a single substitution strategy can provide, within the same catalyst family, members suited to different reaction media.
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BibTeX
@article{poisson2026allterrain,
title = {{An "All-Terrain" Ligand Design Strategy: Phosphorus-Functionalized Nickel Thiosemicarbazones for Hydrogen Evolution in Organic and Aqueous Media}},
author = {Marie Poisson and Michael Papadakis and Foteini Chatzipetri and Anna Katsari and Emmanouil Nikoloudakis and Athanassios G Coutsolelos and Maylis Orio and Renaud Hardré},
journal = {Inorganic Chemistry Frontiers},
year = {2026},
month = oct,
doi = {10.1039/d6qi01982j},
url = {https://hal.science/hal-05820483v1},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - JOUR
TI - An "All-Terrain" Ligand Design Strategy: Phosphorus-Functionalized Nickel Thiosemicarbazones for Hydrogen Evolution in Organic and Aqueous Media
AU - Marie Poisson
AU - Michael Papadakis
AU - Foteini Chatzipetri
AU - Anna Katsari
AU - Emmanouil Nikoloudakis
AU - Athanassios G Coutsolelos
AU - Maylis Orio
AU - Renaud Hardré
PY - 2026
DA - 2026/10/14
JO - Inorganic Chemistry Frontiers
DO - 10.1039/d6qi01982j
UR - https://hal.science/hal-05820483v1
AB - We report the synthesis and characterization of a series of mononuclear nickel thiosemicarbazone complexes bearing phosphorus-functionalized phenyl groups designed to improve their solubility and tune their catalytic properties for hydrogen evolution. NiTSC-PO(OEt)₂ and NiTSC-PO(OH)₂, which carry diethyl phosphonate and phosphonic acid groups, respectively, at the para position of the ligand phenyl rings, were investigated in dimethylformamide using trifluoroacetic acid as the proton source. NiTSC-PO(OH)₂ exhibited notable catalytic activity in aqueous acetate buffer and its photocatalytic performance was further evaluated in combination with nitrogen-doped carbon dots as photosensitizers and a mixture of tris(2-carboxyethyl)phosphine/ascorbic acid as sacrificial electron donor. The two complexes display complementary performances: NiTSC-PO(OEt)2 is the more active electrocatalyst in organic medium, whereas NiTSC-PO(OH)2 operates in water and under photocatalytic conditions. Ligand functionalization thus influences catalytic activity through both solubility and electronic effects, showing that a single substitution strategy can provide, within the same catalyst family, members suited to different reaction media.
SN - 2052-1545
SN - 2052-1553
ER -