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Photostable Polynuclear Ruthenium(II) Photosensitizers Competent for Dehalogenation Photoredox Catalysis at 590 nm. | LitMetric

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Article Abstract

Higher nuclearity photosensitizers produced dehalogenation yields greater than 90% in the reported [Ru(bpy)]-mediated dehalogenation of 4-bromobenzyl-2-chloro-2-phenylacetate to 4-bromobenzyl-2-phenylacetate with orange light in 7 h, whereas after 72 h yields of 49% were obtained with [Ru(bpy)]. Dinuclear (), trinuclear (), and quadrinuclear () ruthenium(II) 2,2'-bipyridine based photosensitizers were synthesized, characterized, and investigated for their photoreactivity. Three main factors were shown to lead to increased yields (i) the red-shifted absorbance of polynuclear photosensitizers, (ii) the more favorable driving force for electron transfer, characterized by more positive (Ru), and (iii) the smaller population of the MC state (<0.5% for , and vs 48% for [Ru(bpy)] at room temperature). Collectively, these results highlight the potential advantages of using polynuclear photosensitizers in phototriggered redox catalysis reactions.

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http://dx.doi.org/10.1021/jacs.0c01503DOI Listing

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