Corrolato(oxo)antimony(V) Dimer with Hydrogen-Bond Donor Groups in Secondary Coordination Sphere as a Catalyst for Hydrogen Evolution Reaction DOI
Rupak Chakraborty, Belarani Ojha,

Tanmoy Pain

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(45), P. 21462 - 21473

Published: Oct. 28, 2024

The focus is on developing alternative molecular catalysts using main-group elements and implementing strategic improvements for sustainable hydrogen production. For this purpose, a FB corrole with (2-(2-((4-methylphenyl)sulfonamido)ethoxy)phenyl) group inserted into the meso position (C-10) of corrole, along its high-valent (corrolato)(oxo)antimony(V) dimer, was synthesized. In crystal structure analysis dimer complex, it noted that sulfonamido in ligand periphery sits atop ring. electrochemical evolution reaction (HER) studied compared previously reported which lacks hydrogen-bond donor groups secondary coordination sphere. newly designed molecules, featuring sphere, demonstrated clear superiority HER. Controlled potential electrolysis employed to evaluate charge accumulation associated generation homogeneous three-electrode system presence 50 mM TFA. produced exhibits Faradaic efficiency approximately 80.96%, turnover frequency (TOF) 0.44 h–1, production rate 52.83 μL highlighting effective catalytic activity evolution.

Language: Английский

Exploring the Potential of Al(III) Photosensitizers for Energy Transfer Reactions DOI Creative Commons
Volkan Caliskanyürek, Anastasiia V. Riabchunova, Stephan Kupfer

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(34), P. 15829 - 15840

Published: Aug. 12, 2024

Three homoleptic Al(III) complexes (Al1–Al3) with different degrees of methylation at the 2-pyridylpyrrolide ligand were systematically tested for their function as photosensitizers (PS) in two types energy transfer reactions. First, generation reactive singlet oxygen (1O2), and second, isomerization (E)- to (Z)-stilbene. 1O2 was directly evidenced by its characteristic NIR emission around 1276 nm indirectly reaction an organic substrate [e.g. 2,5-diphenylfuran (DPF)] using situ UV/vis spectroscopy. In a previous study, presence additional methyl groups found be beneficial photocatalytic reduction CO2 CO, but here Al1 without any exhibits superior performance. To rationalize this behavior, combination photophysical experiments (absorption, excited state lifetimes) together photostability measurements scalar-relativistic time-dependent density functional theory calculations applied. As result, exhibited highest quantum yield (64%), longest lifetime (8.7 ns) best under conditions required reactions (e.g. aerated chloroform). Moreover, provided rate constant (0.043 min–1) oxygenation DPF, outperforming even noble metal-based competitors such [Ru(bpy)3]2+. Finally, enabled long-term test (7 h), which successfully recycled seven times, underlining high potential new class earth-abundant PSs.

Language: Английский

Citations

0

Corrolato(oxo)antimony(V) Dimer with Hydrogen-Bond Donor Groups in Secondary Coordination Sphere as a Catalyst for Hydrogen Evolution Reaction DOI
Rupak Chakraborty, Belarani Ojha,

Tanmoy Pain

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(45), P. 21462 - 21473

Published: Oct. 28, 2024

The focus is on developing alternative molecular catalysts using main-group elements and implementing strategic improvements for sustainable hydrogen production. For this purpose, a FB corrole with (2-(2-((4-methylphenyl)sulfonamido)ethoxy)phenyl) group inserted into the meso position (C-10) of corrole, along its high-valent (corrolato)(oxo)antimony(V) dimer, was synthesized. In crystal structure analysis dimer complex, it noted that sulfonamido in ligand periphery sits atop ring. electrochemical evolution reaction (HER) studied compared previously reported which lacks hydrogen-bond donor groups secondary coordination sphere. newly designed molecules, featuring sphere, demonstrated clear superiority HER. Controlled potential electrolysis employed to evaluate charge accumulation associated generation homogeneous three-electrode system presence 50 mM TFA. produced exhibits Faradaic efficiency approximately 80.96%, turnover frequency (TOF) 0.44 h–1, production rate 52.83 μL highlighting effective catalytic activity evolution.

Language: Английский

Citations

0