Data for Publication "Hydrazine Photorelease from Ru(II) Chugaev-Type Dicarbene Complexes"
<p dir="ltr">Ruthenium(II) polypyridyl complexes exhibit rich excited state reactivity from both photogenerated <sup>3</sup>MLCT and higher energy thermally populated ligand-field (LF) excited states. In order to maximize utility of the different reactivity of these two s...
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2025
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| Sumario: | <p dir="ltr">Ruthenium(II) polypyridyl complexes exhibit rich excited state reactivity from both photogenerated <sup>3</sup>MLCT and higher energy thermally populated ligand-field (LF) excited states. In order to maximize utility of the different reactivity of these two states, the energy gap between them must be tuned without sacrificing the favorable optical and photophysical properties of the complex. In pursuit of photostable Ru<sup>II</sup> complexes for non-dissociative photochemical applications, we herein explore the use of Chugaev-type dicarbene ligands as strong σ-donors. Using a complementary combination of X-ray crystallography, electrochemistry, optical and X-ray spectroscopy, we demonstrate how Chugaev-type dicarbene ligands destabilize LF states of photoactive Ru<sup>II </sup>complexes without sacrificing the favorable optical and photophysical properties of the complex, and compare with π-accepting methylisocyanide ligands. We further report an unexpected dechelative photoelimination of hydrazine from the Ru<sup>II</sup> Chugaev-type dicarbene complexes that occurs directly from the <sup>3</sup>MLCT excited state with quantum yields in the order of ca. 1-5%, and is sensitive to peripheral substitution of chromophoric bipyridine ligands. These findings contribute to growing understanding of molecular design principles for photoactive Ru<sup>II</sup> complexes targeted at either dissociative/non-dissociative photochemical applications, highlight the utility of X-ray spectroscopy as an underused, complementary tool to optical spectroscopy for excited state characterization, and introduce a new potential scaffold and photorelease mechanism for photoactivated chemotherapy.</p> |
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