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Tuning the Electron Storage Potential of a Charge‐Photoaccumulating Ru II Complex by a DFT‐Guided Approach
Author(s) -
Randell Nicholas M.,
Rendon Julia,
Demeunynck Martine,
Bayle PierreAlain,
Gambarelli Serge,
Artero Vincent,
Mouesca JeanMarie,
ChavarotKerlidou Murielle
Publication year - 2019
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.201902312
Subject(s) - oxime , ruthenium , chemistry , electrochemistry , diimine , electron transfer , artificial photosynthesis , electron , photochemistry , redox , computational chemistry , combinatorial chemistry , catalysis , inorganic chemistry , physics , medicinal chemistry , electrode , organic chemistry , photocatalysis , quantum mechanics
Molecular photosensitizers that are able to store multiple reducing equivalents are of great interest in the field of solar fuel production, where most reactions involve multielectronic reduction processes. In order to increase the reducing power of a ruthenium tris‐diimine charge‐photoaccumulating complex, two structural modifications on its fused dipyridophenazine‐pyridoquinolinone ligand were computationally investigated. Addition of an electron‐donating oxime group was calculated to substantially decrease the reduction potentials of the complex, thus guiding the synthesis of a pyridoquinolinone‐oxime derivative. Its spectroscopic and (spectro)electrochemical characterization experimentally confirmed the DFT predictions, with the first and second reduction processes cathodically shifted by −0.24 and −0.14 V, respectively, compared to the parent complex. Moreover, the ability of this novel artificial photosynthetic system to store two photogenerated electrons at a more reducing potential, via a proton‐coupled electron‐transfer mechanism, was demonstrated.