title: Upconverting Nanoparticles Prompt Remote Near-Infrared Photoactivation of Ru(II)-Arene Complexes.
abstract: The synthesis and full characterisation (including X-ray diffraction studies and DFT calculations) of two new piano-stool Ru(II) -arene complexes, namely [(η(6) -p-cym)Ru(bpy)(m-CCH-Py)][(PF)6]2 (1) and [(η(6) -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 [(η(6) -p-cym)Ru(bpy)(P-Trz-Py)][(PF)6]2 (3) and [(η(6) -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 [(η(6) -p-cym)Ru(bpy)(H2O)](2+) and [(η(6) -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.
authors.affiliation: CIC biomaGUNE, Paseo de Miramón182, 20009, Donostia-San Sebastián, Euskadi, Spain.
authors.forename: Emmanuel
authors.initials: E
authors.lastname: Ruggiero
authors.affiliation: Department of Chemistry and NIS Centre of Excellence, University of Turin, via Pietro Giuria 7, 10125, Turin, Italy.
authors.forename: Claudio
authors.initials: C
authors.lastname: Garino
authors.affiliation: CIC biomaGUNE, Paseo de Miramón182, 20009, Donostia-San Sebastián, Euskadi, Spain.|Ikerbasque, Basque Foundation for Science, 48011, Bilbao, Spain.
authors.forename: Juan C
authors.initials: JC
authors.lastname: Mareque-Rivas
authors.affiliation: CIC biomaGUNE, Paseo de Miramón182, 20009, Donostia-San Sebastián, Euskadi, Spain. a.habtemariam@warwick.ac.uk.|Ikerbasque, Basque Foundation for Science, 48011, Bilbao, Spain. a.habtemariam@warwick.ac.uk.|Department of Chemistry, University of Warwick, Coventry, CV4 7AL, UK. a.habtemariam@warwick.ac.uk.
authors.forename: Abraha
authors.initials: A
authors.lastname: Habtemariam
authors.affiliation: CIC biomaGUNE, Paseo de Miramón182, 20009, Donostia-San Sebastián, Euskadi, Spain. lsalassa@cicbiomagune.es.|Kimika Fakultatea, Euskal Herriko Unibertsitatea and Donostia International Physics Center (DIPC) P.K., 1072, Donostia-San Sebastián, Euskadi, Spain. lsalassa@cicbiomagune.es.
authors.forename: Luca
authors.initials: L
authors.lastname: Salassa
keywords: nanoparticles; near-infrared radiation; photoactivation; ruthenium; upconversion