TY - JOUR
T1 - Subtle changes to peripheral ligands enable high turnover numbers for photocatalytic hydrogen generation with supramolecular photocatalysts
AU - Kowacs, T.
AU - O'Reilly, L.
AU - Pan, Qing
AU - Huijser, Jannetje Maria
AU - Lang, P.
AU - Rau, S.
AU - Browne, W.R.
AU - Pryce, M.T.
AU - Vos, J.G.
PY - 2016
Y1 - 2016
N2 - The photocatalytic generation of hydrogen (H2) from protons by two cyclometalated ruthenium–platinum polypyridyl complexes, [Ru(bpy)2(2,5-bpp)PtIS]2+ (1) and [Ru(dceb)2(2,5-bpp)PtIS]2+ (2) [where bpy = 2,2′-bipyridine, 2,5-bpp = 2,2′,5′,2″-terpyridine, dceb = 4,4′-di(carboxyethyl)bipyridine, and S = solvent], is reported. Turnover numbers (TONs) for H2 generation were increased by nearly an order of magnitude by the introduction of carboxyethyl ester units, i.e., from 80 for 1P to 650 for 2P after 6 h of irradiation, with an early turnover frequency (TOF) increasing from 15 to 200 h–1. The TON and TOF values for 2P are among the highest reported to date for supramolecular photocatalysts. The increase correlates with stabilization of the excited states localized on the peripheral ligands of the light-harvesting RuII center.
AB - The photocatalytic generation of hydrogen (H2) from protons by two cyclometalated ruthenium–platinum polypyridyl complexes, [Ru(bpy)2(2,5-bpp)PtIS]2+ (1) and [Ru(dceb)2(2,5-bpp)PtIS]2+ (2) [where bpy = 2,2′-bipyridine, 2,5-bpp = 2,2′,5′,2″-terpyridine, dceb = 4,4′-di(carboxyethyl)bipyridine, and S = solvent], is reported. Turnover numbers (TONs) for H2 generation were increased by nearly an order of magnitude by the introduction of carboxyethyl ester units, i.e., from 80 for 1P to 650 for 2P after 6 h of irradiation, with an early turnover frequency (TOF) increasing from 15 to 200 h–1. The TON and TOF values for 2P are among the highest reported to date for supramolecular photocatalysts. The increase correlates with stabilization of the excited states localized on the peripheral ligands of the light-harvesting RuII center.
KW - IR-101157
KW - METIS-316335
U2 - 10.1021/acs.inorgchem.5b01752
DO - 10.1021/acs.inorgchem.5b01752
M3 - Article
VL - 55
SP - 2685
EP - 2690
JO - Inorganic chemistry
JF - Inorganic chemistry
SN - 0020-1669
IS - 6
ER -