Ruthenium nitrosyl complexes with NO release capability: the use of fluorene as an antenna
Résumé
A ruthenium nitrosyl complex of formula [Ru$^{II}$(fluorene(C6)CH$_2$O-terpy)(bipy)(NO)]$^{3+}$ (AC) in which fluorene(C6) is the 9,9-dihexylfluorene, terpy the 2,2’;6’,2’’-terpyridine, and bipy the 2,2’-bipyridine is presented with its related [Ru$^{II}$(MeO-terpy)(bipy)(NO)]$^{3+}$ (C) and 9,9-dihexylfluorene 2-hydroxymethylfluorene (A) building blocks. The reference complex C undergoes NO release capabilities under irradiations at λ = 365 nm. The effect of the introduction of the fluorescent A antenna within the resulting AC complex is discussed both experimentally and theoretically. The importance of the encaging parameter defined as Φ$_{AC}$ x I$_{AC}$, in which I$_{AC}$ is the quantity of light absorbed by AC and Φ$_{AC}$ the quantum yield of NO release is evidenced and found concentration dependent. The conditions of optimization of the antenna approach to maximize Φ$_{AC}$ x I$_{AC}$ are discussed. The crystal structure of [Ru$^{II}$(fluorene(C6)CH$_2$O-terpy)(bipy)(NO$_2$)](PF6) last intermediate in the synthesis of AC is also presented.
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