title: Photorelease of Pyridyl Esters in Organometallic Ru(II) Arene Complexes.
abstract: New Ru(II) arene complexes of formula [(η6-p-cym)Ru(N-N)(X)]2+ (where p-cym = para-cymene, N-N = 2,2'-bipyrimidine (bpm) or 2,2'-bipyridine (bpy) and X = m/p-COOMe-Py, 1-4) were synthesised and characterized, including the molecular structure of complexes [(η6-p-cym)Ru(bpy)(m-COOMe-Py)]2+ (3) and [(η6-p-cym)Ru(bpy) (p-COOMe-Py)]2+ (4) by single-crystal X-ray diffraction. Complexes 1-4 are stable in the dark in aqueous solution over 48 h and photolysis studies indicate that they can photodissociate the monodentate m/p-COOMe-Py ligands selectively with yields lower than 1%. DFT and TD-DFT calculations (B3LYP/LanL2DZ/6-31G**) performed on singlet and triplet states pinpoint a low-energy triplet state as the reactive state responsible for the selective dissociation of the monodentate pyridyl ligands.
authors.affiliation: CIC biomaGUNE, Donostia-San Sebastián 20009, Spain. a.habtemariam@warwick.ac.uk.|IKERBASQUE, Basque Foundation for Science, Bilbao 48011, 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: Department of Chemistry and NIS Centre of Excellence, University of Turin, Turin 10125, Italy. claudio.garino@unito.it.
authors.forename: Claudio
authors.initials: C
authors.lastname: Garino
authors.affiliation: CIC biomaGUNE, Donostia-San Sebastián 20009, Spain. eruggiero@cicbiomagune.es.
authors.forename: Emmanuel
authors.initials: E
authors.lastname: Ruggiero
authors.affiliation: CIC biomaGUNE, Donostia-San Sebastián 20009, Spain. salonsodecastro@cicbiomagune.es.
authors.forename: Silvia
authors.initials: S
authors.lastname: Alonso-de Castro
authors.affiliation: CIC biomaGUNE, Donostia-San Sebastián 20009, Spain.|IKERBASQUE, Basque Foundation for Science, Bilbao 48011, Spain.
authors.forename: Juan C
authors.initials: JC
authors.lastname: Mareque-Rivas
authors.affiliation: CIC biomaGUNE, Donostia-San Sebastián 20009, Spain. lsalassa@cicbiomagune.es.|Kimika Fakultatea, Euskal Herriko Unibertsitatea and Donostia International Physics Center (DIPC), Donostia-San Sebastián 20080, Spain. lsalassa@cicbiomagune.es.
authors.forename: Luca
authors.initials: L
authors.lastname: Salassa
mesh_terms: D018360:Crystallography, X-Ray; D004952:Esters / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010782:Photolysis; D011725:Pyridines / Q000138:chemical synthesis* / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry*
chemical_list: D004952:Esters; D009942:Organometallic Compounds; D011725:Pyridines; D012428:Ruthenium