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A Noble‐Metal‐Free System for Photocatalytic Hydrogen Production from Water
Author(s) -
Mejía Esteban,
Luo ShuPing,
Karnahl Michael,
Friedrich Aleksej,
Tschierlei Stefanie,
Surkus AnnetteEnrica,
Junge Henrik,
Gladiali Serafino,
Lochbrunner Stefan,
Beller Matthias
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201302091
Subject(s) - triethylamine , quenching (fluorescence) , photochemistry , photocatalysis , chemistry , intramolecular force , hydrogen production , noble metal , excited state , catalysis , hydrogen , chelation , amine gas treating , metal , electron donor , inorganic chemistry , organic chemistry , fluorescence , physics , quantum mechanics , nuclear physics
A series of heteroleptic copper(I) complexes with bidentate $\widehat{PP}$ and $\widehat{NN}$ chelate ligands was prepared and successfully applied as photosensitizers in the light‐driven production of hydrogen, by using [Fe 3 (CO) 12 ] as a water‐reduction catalyst (WRC). These systems efficiently reduces protons from water/THF/triethylamine mixtures, in which the amine serves as a sacrificial electron donor (SR). Turnover numbers (for H) up to 1330 were obtained with these fully noble‐metal‐free systems. The new complexes were electrochemically and photophysically characterized. They exhibited a correlation between the lifetimes of the MLCT excited state and their efficiency as photosensitizers in proton‐reduction systems. Within these experiments, considerably long excited‐state lifetimes of up to 54 μs were observed. Quenching studies with the SR, in the presence and absence of the WRC, showed that intramolecular deactivation was more efficient in the former case, thus suggesting the predominance of an oxidative quenching pathway.