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

Molecules

Abraha Habtemariam¹  Claudio Garino²  Emmanuel Ruggiero¹  Silvia Alonso-de Castro¹  Juan C. Mareque-Rivas¹  Luca Salassa¹ 

[1] CIC biomaGUNE, Donostia–San Sebastián 20009, Spain; E-Mails:;Department of Chemistry and NIS Centre of Excellence, University of Turin, Turin 10125, Italy; E-Mail:

关键词: photoactivatable complexes;    ruthenium;    ruthenium arene;    PDT;    DFT;    photochemistry;   

DOI  :  10.3390/molecules20047276

来源: mdpi

【 摘 要 】

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.

【 授权许可】

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