Link to glow - iEDDA conjugation of a Ruthenium(II) tetrazine complex leading to dihydropyrazine and pyrazine complexes with improved 1O2 formation ability
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Abstract
The synthesis and photophysical properties of the Ru-polypyridyl type complex [(tbbpy)2Ru(bptz)]2+ (Ru-bptz, tbbpy: 4,4’-di-tert-butyl-2,2’-bipyridine, bptz: 2,6-dipyrido-1,2,4,5-tetrazine), and the complexes [(tbbpy)2Ru(L)]2+ formed by inverse electron demand Diels Alder reaction (iEDDA) of Ru-bptz with with alkenes and alkynes, where L is 3,6-dipyrido-2,5-dihydropyridazine (bpdhpn) or 3,6-dipyrido-pyridazine (bppn) are described. A combination of steady-state and time-resolved spectroscopy complemented by the computation of state-specific absorption properties by means of time-dependent density functional theory reveals that the intense visible absorption band stems from Ru → tbbpy and Ru → L metal-to-ligand charge-transfer (MLCT) excitations. The studies show that lowest-lying L-centered MLCT states (3MLCTL) show comparably low emission quantum yields (3–9%) and lifetimes (90–150 ns). This correlates with the singlet oxygen generation ability, following the trend: Ru-bppn > Ru-bpdhpn > Ru-bptz.