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TitleUpconverting Nanoparticles Prompt Remote Near-Infrared Photoactivation of Ru(II)–Arene Complexes
AuthorEmmanuel Ruggiero,Dr. Claudio Garino,Prof. Juan C. Mareque-Rivas,Dr. Abraha Habtemariam, Dr. Luca Salassa
Affiliation(s)CIC biomaGUNE, Donostia-San Sebastián, Euskadi, Spain Kimika Fakultatea, Euskal Herriko Unibertsitatea and Donostia International Physics Center (DIPC) P.K., Donostia-San Sebastián, Euskadi, Spain
PublishedChemistry DOI: 10.1002/chem.201503991
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AbstractThe synthesis and full characterisation (including X-ray diffraction studies and DFT calculations) of two new piano-stool RuII–arene complexes, namely [(η6-p-cym)Ru(bpy)(m-CCH-Py)][(PF)6]2 (1) and [(η6-p-cym)Ru(bpm)(m-CCH-Py)][(PF)6]2 (2; p-cym=p-cymene, bpy=2,2′-bipyridine, bpm=2,2′-bipyrimidine, and m-CCH-Py=3-ethynylpyridine), is described and discussed. The reaction of the m-CCH-Py ligand of 1 and 2 with diethyl-3-azidopropyl phosphonate by Cu-catalysed click chemistry affords [(η6-p-cym)Ru(bpy)(P-Trz-Py)][(PF)6]2 (3) and [(η6-p-cym)Ru(bpm)(P-Trz-Py)][(PF)6]2 (4; P-Trz-Py=[3-(1-pyridin-3-yl-[1,2,3]triazol-4-yl)-propyl]phosphonic acid diethyl ester). Upon light excitation at λ=395 nm, complexes 1–4 photodissociate the monodentate pyridyl ligand and form the aqua adduct ions [(η6-p-cym)Ru(bpy)(H2O)]2+ and [(η6-p-cym)Ru(bpm)(H2O)]2+. Thulium -doped upconverting nanoparticles (UCNPs) are functionalised with 4, thus exploiting their surface affinity for the phosphonate group in the complex. The so-obtained nanosystem UCNP@4 undergoes near-infrared (NIR) photoactivation at λ=980 nm, thus producing the corresponding reactive aqua species that binds the DNA-model base guanosine 5′-monophosphate.Chemisytry

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