Photochemistry of ruthenium(ii) complexes based on 1, 4, 5, 8-tetraazaphenanthrene and 2, 2′-bipyrazine: a comprehensive experimental and theoretical study. Issue 20 (4th May 2017)

• Record Type: Journal Article
• Authors: Kajouj, Sofia; Marcélis, Lionel; Lemaur, Vincent; Beljonne, David; Moucheron, Cécile
• Is Part Of: Dalton transactions. Volume 46:Issue 20(2017)
• Page Start: 6623
• Page End: 6633
• Publication Date: 2017-05-04
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt00620a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Comprehensive study of ruthenium complexes based on 2, 2′-bipyrazine and 1, 4, 5, 8-tetraazaphenanthrene, which can be used as photoreactive materials for biomedical applications. Abstract : Polyazaaromatic ruthenium(ii ) complexes have been largely studied over the last decades, particularly in the scope of the biological applications, for the development of new diagnostic and phototherapeutic agents. In this context, Ru(ii ) complexes able to react with biomolecules upon excitation are of great interest. Photo-oxidizing Ru(ii ) complexes based on π-deficient ligands, such as bpz (2, 2′-bypyrazine) and TAP (1, 4, 5, 8-tetraazaphenathrene), were designed to allow a photo-induced electron transfer (PET) to take place in presence of biomolecules, thanks to their highly photo-oxidizing 3 MLCT state. This PET can occur from either a guanine moiety (G) or a tryptophan residue (Trp) to the excited complex and can ultimately lead to the formation of a photoadduct, i.e. the formation of a covalent bond between the Ru(ii ) complex and the G or Trp moieties of a biomolecule. Here, we report the synthesis of two new photo-oxidizing Ru(ii ) complexes, [Ru(TAP)2 bpz] 2+ and [Ru(bpz)2 TAP] 2+, and the study of their photophysical and electrochemical properties. The influence of the structure of the ligand bpz/TAP on the photophysical and electrochemical properties of the four resulting complexes has been precisely determined thanks to the experimental and theoretical data obtained for to these new complexes.