Photoisomerization and photo-induced nitric oxide release in ruthenium nitrosyl complexes with pyridyl and bipyridyl based ligands / Hasan Shamran Mohammed  

Public ISBD Titre : Photoisomerization and photo-induced nitric oxide release in ruthenium nitrosyl complexes with pyridyl and bipyridyl based ligands Type de document : texte imprimé Auteurs : Hasan Shamran Mohammed, Auteur ; Isabelle Malfant, Auteur Année de publication : 2017 Langues : Anglais (eng) Tags : Complexes de ruthénium à ligand nitrosyle - Complexes à ligand polypyridine - Oxyde nitrique - Photoisomérisation - Photolibération de NO Résumé : "We are interested in the photoactive properties of ruthenium nitrosyl complexes. Ruthenium nitrosyl complexes are well known to possess photochromic properties which arise from the coordination changes of Ru-NO under irradiation at low temperature. This phenomenon has many applications such as high optical data storage and sensors. Ruthenium nitrosyl complexes are also very promising candidates because the photochemical delivery of bioactive small molecules such as nitric oxide (NO•) from ruthenium nitrosyl complexes presents the possibility of controlling the location, timing and dosage of NO• to physiological targets. Nitric oxide photorelease have gained wide attention after the discovery of several nitric oxide physiological functions and its involvement in different cellular processes. This thesis was devoted to studying the factors which affect the photochromic properties and NO photorelease in ruthenium nitrosyl complexes with pyridyl or bipyridyl based ligands. The first chapter of this thesis focuses on a survey of the literature related to both photoisomerization and photorelease phenomena. In chapter 2, the synthesis and characterization of ruthenium nitrosyl complexes with pyridyl based ligands with the formula trans(X,NO)-[Ru(R-py)4XNO](PF6)2, (where R-py is pyridine, 4-picoline, 3-picoline, 4-vinylpyridine, 3-carboxaldhydepyridine and 4-chloropyridine, X=Cl, Br, I or OH) are discussed. In chapter 3, the synthesis and characterization of ruthenium nitrosyl complexes with bipyridyl based ligand with formula cis(X,NO)-[Ru(L)2XNO]Y2, (L= 2,2'-bipyridine or 4,4'-dimethyl-2,2'-bipyridine, X=Cl, NO2 or Br, Y=PF6 or Br) are discussed. In chapter 4, we present the results of our investigations of nitrosyl ligand photoisomerization in Ru-NO with pyridyl and bipyridyl ligands. The conversion of Ru-NO to Ru-ON conformation was estimated by infrared spectroscopy upon irradiation by blue light at low temperature in the solid state. The values are ranged between 1-76%. We studied the effects of cis/trans ligand position to nitrosyl and the nature of substituents on pyridine or bipyridine ligand (electron donating or withdrawing group). We used theoretical calculations (DFT) to explain the different photochromic properties between parent complex with a pyridine ligand and 4-chloropyridine ligand. The fifth chapter is devoted to the study of NO photorelease. The quantum yield (NO) was estimated in the range of 0.2-0.7. Griess test was used to confirm NO delivery." Document : Thèse de Doctorat Etablissement_delivrance : Université de Toulouse Date_soutenance : 21/09/2017 Ecole_doctorale : École doctorale Sciences de la Matière (Toulouse) Domaine : Chimie organométallique de coordination En ligne : http://thesesups.ups-tlse.fr/3640/ Photoisomerization and photo-induced nitric oxide release in ruthenium nitrosyl complexes with pyridyl and bipyridyl based ligands [texte imprimé] / Hasan Shamran Mohammed, Auteur ; Isabelle Malfant, Auteur . - 2017. Langues : Anglais (eng) Tags : Complexes de ruthénium à ligand nitrosyle - Complexes à ligand polypyridine - Oxyde nitrique - Photoisomérisation - Photolibération de NO Résumé : "We are interested in the photoactive properties of ruthenium nitrosyl complexes. Ruthenium nitrosyl complexes are well known to possess photochromic properties which arise from the coordination changes of Ru-NO under irradiation at low temperature. This phenomenon has many applications such as high optical data storage and sensors. Ruthenium nitrosyl complexes are also very promising candidates because the photochemical delivery of bioactive small molecules such as nitric oxide (NO•) from ruthenium nitrosyl complexes presents the possibility of controlling the location, timing and dosage of NO• to physiological targets. Nitric oxide photorelease have gained wide attention after the discovery of several nitric oxide physiological functions and its involvement in different cellular processes. This thesis was devoted to studying the factors which affect the photochromic properties and NO photorelease in ruthenium nitrosyl complexes with pyridyl or bipyridyl based ligands. The first chapter of this thesis focuses on a survey of the literature related to both photoisomerization and photorelease phenomena. In chapter 2, the synthesis and characterization of ruthenium nitrosyl complexes with pyridyl based ligands with the formula trans(X,NO)-[Ru(R-py)4XNO](PF6)2, (where R-py is pyridine, 4-picoline, 3-picoline, 4-vinylpyridine, 3-carboxaldhydepyridine and 4-chloropyridine, X=Cl, Br, I or OH) are discussed. In chapter 3, the synthesis and characterization of ruthenium nitrosyl complexes with bipyridyl based ligand with formula cis(X,NO)-[Ru(L)2XNO]Y2, (L= 2,2'-bipyridine or 4,4'-dimethyl-2,2'-bipyridine, X=Cl, NO2 or Br, Y=PF6 or Br) are discussed. In chapter 4, we present the results of our investigations of nitrosyl ligand photoisomerization in Ru-NO with pyridyl and bipyridyl ligands. The conversion of Ru-NO to Ru-ON conformation was estimated by infrared spectroscopy upon irradiation by blue light at low temperature in the solid state. The values are ranged between 1-76%. We studied the effects of cis/trans ligand position to nitrosyl and the nature of substituents on pyridine or bipyridine ligand (electron donating or withdrawing group). We used theoretical calculations (DFT) to explain the different photochromic properties between parent complex with a pyridine ligand and 4-chloropyridine ligand. The fifth chapter is devoted to the study of NO photorelease. The quantum yield (NO) was estimated in the range of 0.2-0.7. Griess test was used to confirm NO delivery." Document : Thèse de Doctorat Etablissement_delivrance : Université de Toulouse Date_soutenance : 21/09/2017 Ecole_doctorale : École doctorale Sciences de la Matière (Toulouse) Domaine : Chimie organométallique de coordination En ligne : http://thesesups.ups-tlse.fr/3640/

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