Assemblages de coordination de platine(II) à ligands métallo-quinonoïdes : conception, luminescence et chiralité

The PhD research work presented herein deals with the use of organometallic ligands as connectors to luminescent organometallic building blocks to provide novel luminescent coordination assemblies. These organometallic ligands, called "organometalloligands" are sandwich-complexes where a ruthenium(II) or an iridium(III) is pi-bonded to a carbo-cycle bearing one or two chelating ligands. These ligands are either sulfur or selenium atoms. The luminescent building blocks are basically cyclometallated platinum(II) or polypyridyl Pt(II) moieties. Upon variation of the geometrical structures of the organometalloligands as well as the platinum luminophores, various polynuclear assemblies displaying unique appealing architectures are obtained. Moreover for each type of coordination assembly, a full investigation of their absorption and emission properties is presented. For instance, such assemblies with organometalloligand spacer display 1D infinite chains, where the individual units exhibit supramolecular Pt···Pt and pi-pi interactions. On the other hand, the non-innocent character of the pi-bonded dithiolene ligand is controlled as it is shown by electrochemistry experiments. Finally, the synthesis of a novel organometalloligand bearing chiral function allows, the control of the chirality of the assemblies, the modulation of the intermolecular Pt···Pt and pi-pi interactions and overall their luminescent properties.Les travaux de recherche doctorale présentés dans ce manuscrit traitent de l'utilisation de ligands organométalliques associés à des briques organométalliques luminophores. Ces ligands rganométalliques, appelés organométalloligands sont des complexes sandwichs où un ruthénium(II) ou un iridium(III) est -coordonné à un cycle portant une ou deux fonctions chélatantes. Ces fonctions sont des atomes de soufre ou de sélénium. Les briques luminophores sont constituées d'un atome de platine(II) complexé par des ligands aromatiques. En faisant varier la topologie des organométalloligands employés ainsi que le type de briques de platine, des assemblages polynucléaires variés sont obtenus. Pour chaque famille d'assemblages synthétisés, une étude des propriétés d'absorption et de luminescence est menée. Au travers de ces divers assemblages, différents aspects particulier de la chimie de coordination sont mis en avant. Ainsi, nous pouvons avec un organométalloligand servant d'espaceur créer des chaînes monodimensionnelles, leur formation étant assurée par des interactions de type supramoléculaires Pt···Pt et - . La stratégie de l'organométalloligand permet par ailleurs d'amoindrir le caractère non-innocent d'un ligand dithiolène complexé à une brique de platine luminescente, ce qui peut être confirmé par étude électrochimique. Enfin, la synthèse d'un organométalloligand portant une information chirale mène, en contrôlant cette chiralité, à moduler les agrégations intermoléculaires ce qui permet d'observer une modulation en terme de luminescence

A Convenient Approach to Luminescent Cyclometalated Platinum(II) Complexes with Organometallic π-Bonded Benzenedithiolate

International audienceA family of neutral cyclometalated platinum(II) complexes [(C^N)Pt(η-S^S)] with π-bonded benzenedithiolate {(η-S^S) = Cp*Ru(C6H4S2)} and various cyclometalated ligands, {(C^N) = 2-phenylpyridine (ppy), (2); 2,4-difluorophenylpyridine (F2ppy) (3), benzo[h]quinoline (bzq) (4); dibenzo[f,h]quinoline (dbzq) (5) } were prepared and fully characterized. For comparison purposes the related bipyridine platinum (II) complex [(bpy)Pt(η-S^S)][OTf] (6) was also prepared. The electrochemistry behavior of these complexes was investigated and shows the enhanced stability of these compounds toward oxidation due to the presence of Cp*Ru moiety which is now π-bonded to the benzenedithiolato group. Moreover several complexes were identified by single crystal X-ray molecular structures. To the best of our knowledge these are the first structures to be reported for cyclometalated platinum complexes with a π-bonded benzenedithiolate (bdt) ligand. All of the complexes are luminescent in fluid solution at room temperature and in glassy solution at 77 K; their emission properties can be tuned through ligand variation

Coordination platinum(II) assemblies imparted from metallo-quinonoid ligands : design, luminescence and chirality

Les travaux de recherche doctorale présentés dans ce manuscrit traitent de l'utilisation de ligands organométalliques associés à des briques organométalliques luminophores. Ces ligands rganométalliques, appelés organométalloligands sont des complexes sandwichs où un ruthénium(II) ou un iridium(III) est -coordonné à un cycle portant une ou deux fonctions chélatantes. Ces fonctions sont des atomes de soufre ou de sélénium. Les briques luminophores sont constituées d'un atome de platine(II) complexé par des ligands aromatiques. En faisant varier la topologie des organométalloligands employés ainsi que le type de briques de platine, des assemblages polynucléaires variés sont obtenus. Pour chaque famille d'assemblages synthétisés, une étude des propriétés d'absorption et de luminescence est menée. Au travers de ces divers assemblages, différents aspects particulier de la chimie de coordination sont mis en avant. Ainsi, nous pouvons avec un organométalloligand servant d'espaceur créer des chaînes monodimensionnelles, leur formation étant assurée par des interactions de type supramoléculaires Pt···Pt et - . La stratégie de l'organométalloligand permet par ailleurs d'amoindrir le caractère non-innocent d'un ligand dithiolène complexé à une brique de platine luminescente, ce qui peut être confirmé par étude électrochimique. Enfin, la synthèse d'un organométalloligand portant une information chirale mène, en contrôlant cette chiralité, à moduler les agrégations intermoléculaires ce qui permet d'observer une modulation en terme de luminescence.The PhD research work presented herein deals with the use of organometallic ligands as connectors to luminescent organometallic building blocks to provide novel luminescent coordination assemblies. These organometallic ligands, called "organometalloligands" are sandwich-complexes where a ruthenium(II) or an iridium(III) is pi-bonded to a carbo-cycle bearing one or two chelating ligands. These ligands are either sulfur or selenium atoms. The luminescent building blocks are basically cyclometallated platinum(II) or polypyridyl Pt(II) moieties. Upon variation of the geometrical structures of the organometalloligands as well as the platinum luminophores, various polynuclear assemblies displaying unique appealing architectures are obtained. Moreover for each type of coordination assembly, a full investigation of their absorption and emission properties is presented. For instance, such assemblies with organometalloligand spacer display 1D infinite chains, where the individual units exhibit supramolecular Pt···Pt and pi-pi interactions. On the other hand, the non-innocent character of the pi-bonded dithiolene ligand is controlled as it is shown by electrochemistry experiments. Finally, the synthesis of a novel organometalloligand bearing chiral function allows, the control of the chirality of the assemblies, the modulation of the intermolecular Pt···Pt and pi-pi interactions and overall their luminescent properties

Dinuclear (N^∧C^∧N) Pincer Pt(II) Complexes with Bridged Organometallic Linkers: Synthesis, Structures, Self-Aggregation, and Photophysical Properties

International audienceA new family of cationic dinuclear cyclometalated Pt(II) complexes containing an organometallic assembling ligand has been reported. The general formulas for these compounds is as follow: [R-(N∧C∧N)Pt—L-L—Pt(N∧C∧N)-R][X]2, where L-L = [Cp*Ir-p-(η4-C6H4S2)], R = H, X = OTf (5); R= CF3–, X = OTf (6a), SbF6 (6b); L-L = [Cp*Ir-p-(η4-C6H4Se2)] R= CF3–, X = OTf (7a), SbF6 (7b). In these coordination assemblies two cyclometalated R-(N∧C∧N)Pt moieties are held by either η4-dithio-p-benzoquinone complex [Cp*Ir-p-(η4-C6H4S2)] (3) or η4-diseleno-p-benzoquinone complex [Cp*Ir-p-(η4-C6H4Se2)] (4). The molecular structures of the known complex [4-CF3-(N∧C∧N)PtCl] as well as two compounds of the above family [(N∧C∧N)Pt–Cp*Ir-p-(η4-C6H4S2)—Pt(N∧C∧N)][CF3SO3]2 (5) and [CF3-(N∧C∧N)Pt—Cp*Ir-p-(η4-C6H4S2)—Pt(N∧C∧N)-CF3][CF3SO3]2 (6a) were ascertained by single crystal X-ray diffraction study and confirmed the formation of the target molecules. The solid-state packing of 5 and 6a confirms the presence π–π and short Pt···Pt interactions among individual units providing 1D supramolecular chains. To our knowledge, these are the only known examples where two cyclometalated Pt(N∧C∧N) units are assembled by a bridging ligand (vide infra). All compounds show phosphorescence in the bluish-green region (486–521 nm) in the solution at room temperature and exhibit higher luminescence quantum yields relative to the analogous compounds containing a Pt(terpy) chromophore in thin film

A unique class of neutral cyclometalated platinum(<scp>ii</scp>) complexes with π-bonded benzenedithiolate: synthesis, molecular structures and tuning of luminescence properties

A unique class of luminescent neutral cyclometalated platinum(ii) complexes 2–4 with π-bonded benzenedithiolate are reported including two X-ray molecular structures.</p

Rational Design of Mono- and Bi-Nuclear Cyclometalated Ir(III) Complexes Containing Di-Pyridylamine Motifs: Synthesis, Structure, and Luminescent Properties

Heteroleptic cyclometalated iridium (III) complexes (1&ndash;3) containing di-pyridylamine motifs were prepared in a stepwise fashion. The presence of the di-pyridylamine ligands tunes their electronic and optical properties, generating blue phosphorescent emitters at room temperature. Herein we describe the synthesis of the mononuclear iridium complexes [Ir(ppy)2(DPA)][OTf] (1), (ppy = phenylpyridine; DPA = Dipyridylamine) and [Ir(ppy)2(DPA-PhI)][OTf] (2), (DPA-PhI = Dipyridylamino-phenyliodide). Moreover, the dinuclear iridium complex [Ir(ppy)2(L)Ir(ppy)2][OTf]2 (3) containing a rigid angular ligand &ldquo;L = 3,5-bis[4-(2,2&prime;-dipyridylamino)phenylacetylenyl]toluene&rdquo; and displaying two di-pyridylamino groups was also prepared. For comparison purposes, the related dinuclear rhodium complex [Rh (ppy)2(L)Rh(ppy)2][OTf]2 (4) was also synthesized. The x-ray molecular structure of complex 2 was reported and confirmed the formation of the target molecule. The rhodium complex 4 was found to be emissive only at low temperature; in contrast, all iridium complexes 1&ndash;3 were found to be phosphorescent in solution at 77 K and room temperature, displaying blue emissions in the range of 478&ndash;481 nm

Ester-substituted cyclometallated rhodium and iridium coordination assemblies with π-bonded dioxolene ligand: synthesis, structures and luminescent properties

A series of functionalized cyclometallated rhodium and iridium coordination assemblies2–7displaying a π-bonded dioxolene ligand is described.</p

Énergie et recyclage

Recherche sur la relation entre le système énergétique et la forme de la ville et du territoire, à partir de deux cas d’étude : l’aire métropolitaine du Grand Paris et la Vénétie