Photophysical Properties of Ruthenium(II) Polypyridyl DNA Intercalators: Effects of the Molecular Surroundings Investigated by Theory

The environmental effects on the structural and photophysical properties of [Ru(L)2(dppz)]2+ complexes (L=bpy=2,2′‐bipyridine, phen=1,10‐phenanthroline, tap=1,4,5,8‐tetraazaphenanthrene; dppz=dipyrido[3,3‐a:2′,3′‐c]phenazine), used as DNA intercalators, have been studied by means of DFT, time‐depend...

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Vydáno v:	Chemistry : a European journal Ročník 20; číslo 40; s. 12901 - 12909
Hlavní autoři:	Véry, Thibaut, Ambrosek, David, Otsuka, Miho, Gourlaouen, Christophe, Assfeld, Xavier, Monari, Antonio, Daniel, Chantal
Médium:	Journal Article
Jazyk:	angličtina
Vydáno:	Weinheim WILEY-VCH Verlag 26.09.2014 WILEY‐VCH Verlag Wiley Subscription Services, Inc Wiley-VCH Verlag
Témata:	2,2'-Dipyridyl - chemistry 2,2'-Dipyridyl - pharmacology Acetonitrile Chemical Sciences Chemistry Density Deoxyribonucleic acid DNA DNA - chemistry Electronics Environment effects Environmental effects Excitation Intercalating Agents - chemistry Intercalating Agents - pharmacology intercalations Ligands Luminescence Mathematical analysis Models, Molecular Organometallic Compounds - chemistry Organometallic Compounds - pharmacology Phenanthrenes - chemistry Phenanthrenes - pharmacology Phenanthrolines - chemistry Phenanthrolines - pharmacology Phenazines - chemistry Phenazines - pharmacology photophysics quantum chemistry Ruthenium Ruthenium - chemistry Ruthenium - pharmacology Theory quantum chemistry ruthenium photophysics DNA intercalations
ISSN:	0947-6539, 1521-3765, 1521-3765
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Shrnutí:	The environmental effects on the structural and photophysical properties of [Ru(L)2(dppz)]2+ complexes (L=bpy=2,2′‐bipyridine, phen=1,10‐phenanthroline, tap=1,4,5,8‐tetraazaphenanthrene; dppz=dipyrido[3,3‐a:2′,3′‐c]phenazine), used as DNA intercalators, have been studied by means of DFT, time‐dependent DFT, and quantum mechanics/molecular mechanics calculations. The electronic characteristics of the low‐lying triplet excited states in water, acetonitrile, and DNA have been investigated to decipher the influence of the environment on the luminescent behavior of this class of molecules. The lowest triplet intra‐ligand (IL) excited state calculated at λ≈800 nm for the three complexes and localized on the dppz ligand is not very sensitive to the environment and is available for electron transfer from a guanine nucleobase. Whereas the lowest triplet metal‐to‐ligand charge‐transfer (3MLCT) states remain localized on the ancillary ligand (tap) in [Ru(tap)2(dppz)]2+, regardless of the environment, their character is drastically modified in the other complexes [Ru(phen)2(dppz)]2+ and [Ru(bpy)2(dppz)]2+ upon going from acetonitrile (MLCTdppz/phen or MLCTdppz/bpy) to water (MLCTdppz) and DNA (MLCTphen and MLCTbpy). The change in the character of the low‐lying 3MLCT states accompanying nuclear relaxation in the excited state controls the emissive properties of the complexes in water, acetonitrile, and DNA. The light‐switching effect has been rationalized on the basis of environment‐induced control of the electronic density distributed in the lowest triplet excited states. Get in there! The environmental effects on the structural and photophysical properties of [Ru(L)2(dppz)]2+ complexes (L=bpy=2,2′‐bipyridine, phen=1,10‐phenanthroline, tap=1,4,5,8‐tetraazaphenanthrene; dppz=dipyrido[3,3‐a:2′,3′‐c]phenazine), used as DNA intercalators, have been studied theoretically (see figure).
Bibliografie:	Université Louis Pasteur Campus France program of the French Embassy in Japan istex:E5F1629AA3245A0B87BA3FAF9905C51023751B88 International Center for Frontier Research in Chemistry (FRC, Strasbourg) CNRS ANR program - No. ANR-09-BLAN-0191-01 Perspect-H2O "Chaire d'excellence" program ArticleID:CHEM201402963 European COST actions CODEC ark:/67375/WNG-4603VSX8-N ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23
ISSN:	0947-6539 1521-3765 1521-3765
DOI:	10.1002/chem.201402963