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Photorelease of Pyridyl Esters in Organometallic Ru(II) Arene Complexes

CIC biomaGUNE, Donostia–San Sebastián 20009, Spain
IKERBASQUE, Basque Foundation for Science, Bilbao 48011, Spain
Department of Chemistry, University of Warwick, Coventry CV4 7AL, UK
Department of Chemistry and NIS Centre of Excellence, University of Turin, Turin 10125, Italy
Kimika Fakultatea, Euskal Herriko Unibertsitatea and Donostia International Physics Center (DIPC), Donostia–San Sebastián 20080, Spain
Author to whom correspondence should be addressed.
Academic Editor: Iztok Turel
Molecules 2015, 20(4), 7276-7291;
Received: 20 February 2015 / Revised: 14 April 2015 / Accepted: 15 April 2015 / Published: 21 April 2015
(This article belongs to the Special Issue Practical Applications of Metal Complexes)
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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, 14) 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 14 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. View Full-Text
Keywords: photoactivatable complexes; ruthenium; ruthenium arene; PDT; DFT; photochemistry photoactivatable complexes; ruthenium; ruthenium arene; PDT; DFT; photochemistry

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Habtemariam, A.; Garino, C.; Ruggiero, E.; Alonso-de Castro, S.; Mareque-Rivas, J.C.; Salassa, L. Photorelease of Pyridyl Esters in Organometallic Ru(II) Arene Complexes. Molecules 2015, 20, 7276-7291.

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