Functionalized Ruthenium Complexes: Selective “Turn-on” Detection of Biologically Relevant Anionic Species

Emanuela Berni (1) , Laurent Le Henaff (1) , Lucie Jarrige (1) , Emeline Girard (1) , Gediminas Jonusauskas (2) , Isabelle Gosse (1) , Sandra Pinet (1)

1 ISM - Institut des Sciences Moléculaires
2 LOMA - Laboratoire Ondes et Matière d'Aquitaine

To study the effect of the structure of 3,3′-modified bipyridyl ruthenium complexes on their ability to recognize organic anions, various ruthenium complexes have been prepared. The binding functions and large-sized modified bipyridyl ligand turned out to be essential for selectivity in acetonitrile. The selectivity for dicarboxylates or phosphates can be switched by using guanidinium- or ammonium-functionalized probes. One of these probes turned out to be selective towards glutamate over aspartate and γ-aminobutyric acid (GABA). Another was selective towards adenosine 5′-triphosphate (ATP) over adenosine 5′-diphosphate (ADP), pyrophosphate (PPi), adenosine 5′-monophosphate (AMP), and orthophosphate (Pi). In both cases, the binding was attributed to coulombic interactions and hydrogen bonding. π-stacking interactions also occurred with nucleotides. Replacing ammonium by zinc-dipicolylamine units made possible the recognition of phosphorylated species in buffered aqueous systems. To our delight, this probe showed selectivity for ADP over ATP and we proved that the selectivity was partly due to substitution at the 3- and 3′-positions of the ligand.

Mots clés: Molecular recognition; Luminescence; Ruthenium; Glutamate; Nucleotides

Domaines: Chimie de coordination

Emanuela Berni, Laurent Le Henaff, Lucie Jarrige, Emeline Girard, Gediminas Jonusauskas, et al.. Functionalized Ruthenium Complexes: Selective “Turn-on” Detection of Biologically Relevant Anionic Species. European Journal of Organic Chemistry, 2017, 2017 (25), pp.3620-3630. ⟨10.1002/ejoc.201700586⟩. ⟨hal-01569750⟩