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Luminescence and Light‐Driven Energy and Electron Transfer from an Exceptionally Long‐Lived Excited State of a Non‐Innocent Chromium(III) Complex
Author(s) -
Treiling Steffen,
Wang Cui,
Förster Christoph,
Reichenauer Florian,
Kalmbach Jens,
Boden Pit,
Harris Joe P.,
Carrella Luca M.,
Rentschler Eva,
ReschGenger Ute,
Reber Christian,
Seitz Michael,
Gerhards Markus,
Heinze Katja
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201909325
Subject(s) - excited state , photochemistry , chromophore , chemistry , luminescence , quantum yield , redox , ruthenium , electron transfer , bipyridine , chromium , inorganic chemistry , crystallography , materials science , crystal structure , fluorescence , atomic physics , organic chemistry , physics , optoelectronics , quantum mechanics , catalysis
Photoactive metal complexes employing Earth‐abundant metal ions are a key to sustainable photophysical and photochemical applications. We exploit the effects of an inversion center and ligand non‐innocence to tune the luminescence and photochemistry of the excited state of the [CrN 6 ] chromophore [Cr(tpe) 2 ] 3+ with close to octahedral symmetry (tpe=1,1,1‐tris(pyrid‐2‐yl)ethane). [Cr(tpe) 2 ] 3+ exhibits the longest luminescence lifetime ( τ =4500 μs) reported up to date for a molecular polypyridyl chromium(III) complex together with a very high luminescence quantum yield of Φ =8.2 % at room temperature in fluid solution. Furthermore, the tpe ligands in [Cr(tpe) 2 ] 3+ are redox non‐innocent, leading to reversible reductive chemistry. The excited state redox potential and lifetime of [Cr(tpe) 2 ] 3+ surpass those of the classical photosensitizer [Ru(bpy) 3 ] 2+ (bpy=2,2′‐bipyridine) enabling energy transfer (to oxygen) and photoredox processes (with azulene and tri( n ‐butyl)amine).