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Upconverting Nanoparticles Prompt Remote Near‐Infrared Photoactivation of Ru(II)–Arene Complexes
Author(s) -
Ruggiero Emmanuel,
Garino Claudio,
MarequeRivas Juan C.,
Habtemariam Abraha,
Salassa Luca
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201503991
Subject(s) - chemistry , phosphonate , denticity , adduct , ligand (biochemistry) , medicinal chemistry , stereochemistry , ruthenium , bipyridine , crystallography , guanosine , catalysis , crystal structure , receptor , organic chemistry , biochemistry
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)(H 2 O)] 2+ and [(η 6 ‐ p ‐cym)Ru(bpm)(H 2 O)] 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.