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Luminescent Lanthanide Architectures for Applications in Optoelectronics Eugen S

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Luminescent Lanthanide Architectures for Applications in Optoelectronics Eugen S Luminescent lanthanide architectures for applications in optoelectronics Eugen S. Andreiadis To cite this version: Eugen S. Andreiadis. Luminescent lanthanide architectures for applications in optoelectronics. Chem- ical Sciences. Université Joseph-Fourier - Grenoble I, 2009. English. tel-00383968 HAL Id: tel-00383968 https://tel.archives-ouvertes.fr/tel-00383968 Submitted on 13 May 2009 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. École Doctorale Chimie et Sciences du Vivant THESE Pour obtenir le grade de DOCTEUR DE L’UNIVERSITE JOSEPH FOURIER Discipline : CHIMIE ORGANIQUE Présentée par Eugen S. ANDREIADIS EDIFICES LUMINESCENTS A BASE DE LANTHANIDES POUR L’OPTO-ELECTRONIQUE Thése soutenue le 28 avril 2009 Composition du jury Prof. Luisa DE COLA Université de Münster Rapporteur Prof. Jean WEISS Université de Strasbourg Rapporteur Prof. Muriel HISSLER Université de Rennes Examinateur Dr. Guy ROYAL Université de Grenoble Examinateur Dr. Marinella MAZZANTI CEA Grenoble Directeur de thèse Dr. Renaud DEMADRILLE CEA Grenoble Co‐directeur de thèse Service de Chimie Inorganique et Biologique Institut Nanosciences et Cryogénie, CEA Grenoble, France École Doctorale Chimie et Sciences du Vivant THESIS For obtaining the degree of DOCTOR OF PHILOSOPHY OF THE JOSEPH FOURIER UNIVERSITY Specialty : ORGANIC CHEMISTRY Presented by Eugen S. ANDREIADIS LUMINESCENT LANTHANIDE ARCHITECTURES FOR APPLICATIONS IN OPTOELECTRONICS Thesis defended on 28 April 2009 Composition of jury Prof. Luisa DE COLA University of Münster Rapporteur Prof. Jean WEISS University of Strasbourg Rapporteur Prof. Muriel HISSLER University of Rennes Examinator Dr. Guy ROYAL University of Grenoble Examinator Dr. Marinella MAZZANTI CEA Grenoble Thesis director Dr. Renaud DEMADRILLE CEA Grenoble Thesis co‐director Service de Chimie Inorganique et Biologique Institut Nanosciences et Cryogénie, CEA Grenoble, France Résumé Les complexes luminescents de lanthanides font l’objet d’une recherche importante dans le domaine de l’opto-électronique du fait de couleur pure et de rendements quantiques importants. Le développement de nouveaux chelates spécifiquement adaptés pour des applications opto- électroniques reste cependant un domaine moins développé par rapport à d’autres applications. Le but de ce travail est d'accéder à de nouvelles possibilités de synthèse dans le domaine des émetteurs moléculaires à base de lanthanides pour l’opto-electronique ; ceci, en concevant de nouveaux ligands adaptés à la complexation de ces métaux et l’étude des propriétés optiques des complexes formés. A cette fin nous avons synthétisés et étudiés une série de ligands basés sur des motifs terpyridine-, bipyridine- et pyridine-tetrazole. Divers substituants ont été ajoutés afin de moduler les propriétés électroniques de ces molécules avec, pour résultats, l’obtention de fortes efficacités lumineuses pour certains de ces complexes tant dans le visible que le proche infrarouge. Les effets induits par l’ajout des divers subtituants sur leurs propriétés photophysiques ont été clairement démontré. De plus, nous avons également synthétisés et testé en couche active de dispositifs OLED une nouvelle classe de complexes neutres complétées par des unités dicétonates. Nous avons par ailleurs explorés la sensibilisation des ions lanthanides par l’intermédiaire de complexes de métaux de transition d. Pour cela nous avons conçus une nouvelle architecture hétéro-métallique d-f où le complexe d’iridium est employé comme antenne. Finalement, nous avons étudiés les processus de transfert d’énergie par mesures de luminescence. Mots-clés lanthanide, opto-électronique, OLED, complexe, tétrazole, luminescence, europium, terbium, néodyme, iridium, hétéronucléaire, héterométallique, greffage. Discipline Chimie organique et chimie de coordination Laboratoire Laboratoire de Reconnaissance Ionique et Chimie de Coordination Service de Chimie Inorganique et Biologique, UMR-E3 CEA-UJF Institut Nanosciences et Cryogénie, CEA Grenoble 17 Rue des Martyrs, 38054 Grenoble Cedex, France v vi Abstract Luminescent lanthanide complexes are receiving a large interest for their applications in the field of optoelectronics, as a result of their pure colors and high emission efficiencies. However, the development of new lanthanide chelates for optoelectronic devices has lagged behind that of other applications, and only a limited number of architectures have been tested. The aim of this work is to access new synthetic possibilities in the area of lanthanide emitters for optoelectronics, by designing specific ligands and studying the properties of their lanthanide complexes, considering their applications for solid state devices. To achieve this aim, we have designed, synthesized and studied the complexation of lanthanides by a series of ligands based on the terpyridine-, bipyridine- and pyridine-tetrazole motifs, appended with substituents having various electronic effects. The resulting complexes have been characterized by X-ray crystallography, NMR and luminescence studies. The emission efficiencies are very high in some cases, both in the visible and in the NIR region, demonstrating the clear influence of tuning the ligand structure on the photophysical properties of the final lanthanide complexes. Furthermore, we have synthesized, characterized and tested in OLED devices a new class of neutral complexes completed by β-diketonate units. Finally, in order to explore the sensitization of lanthanide ions by d-metal complexes, we have designed and synthesized, based on our previous studies, a new specific heterometallic architecture containing iridium complexes as lanthanide antennas, and we have investigated by luminescence measurements the energy transfer processes. Keywords lanthanide, optoelectronic, OLED, complex, tetrazole, luminescence, europium, terbium, neodymium, iridium, heteronuclear, heterometallic, grafting Specialty Organic chemistry and coordination chemistry Laboratory Laboratoire de Reconnaissance Ionique et Chimie de Coordination Service de Chimie Inorganique et Biologique, UMR-E3 CEA-UJF Institut Nanosciences et Cryogénie, CEA Grenoble 17 Rue des Martyrs, 38054 Grenoble Cedex, France vii viii Acknowledgements I am very grateful to Dr. Marinella Mazzanti for having given me the opportunity to work on a fascinating and interdisciplinary project and especially for having directed me with clear and useful advices, as well as given me the independence for managing the research details on my own. I would also like to thank sincerely Dr. Renaud Demadrille as thesis co-director, whose help and support during these three years were essential to me. I would like to express my gratitude to Professor Luisa De Cola, Professor Jean Weiss, Professor Muriel Hissler and Dr. Guy Royal for accepting to judge the quality of my work. Particular thanks are addressed to Dr. Daniel Imbert for his help and advices during the preparation of the thesis manuscript and the public defense. I would like to acknowledge also the following persons for their fundamental contribution to this work: - Dr. Jacques Pécaut for the X-ray diffraction measurements and the resolution of crystal structures; - Dr. Daniel Imbert for the photophysical characterization of complexes and for having initiated me in the luminescence measurements; - Dr. Bruno Jousselme, Professor Alexander Fisyuk, Yann Kervella and Zaireen Yahya for the organic synthesis of some precursors and ligands; - Adrian Calborean for the DFT calculations on iridium complexes; - Colette Lebrun for the ES-MS analysis of the compounds; - Pierre-Alain Bayle for help with the NMR measurements; - Dr. Pascal Viville for the preliminary testing of the lanthanide complexes in OLED devices. Many thanks to former and present collaborators at the RICC Laboratory for their practical help, friendly support and encouragement during these years. Last but not least, I would like to thank my family and friends for their long-lasting patience and support. The European Community through the Marie Curie CHEMtronics programme (MEST-CT-2005- 020513) is deeply acknowledged for financial support. ix x Résumé étendu en français a) Introduction Les lanthanides sont les 15 éléments de la première période du bloc f, allant du lanthane (Z = 57) au lutécium (Z = 71). Les orbitales 4f ont une faible extension radiale et sont blindées par les couches externes 5s25p6 qui les protègent des perturbations extérieures. Ainsi, les électrons de valence 4f sont peu sensibles à leur environnement chimique et la formation d’une liaison chimique par interaction covalente impliquant des électrons 4f est impossible. L’interaction métal-ligand dans les complexes de Ln(III) est donc décrite par un modèle purement ionique avec une excellente précision. De plus, les ions lanthanides sont des acides durs dans la classification de Pearson. Ils interagissent préférentiellement avec des ligands durs, contenant par exemple des atomes d’oxygène donneurs (eau, carboxylates). Une autre conséquence de l’enfouissement des orbitales f dans le nuage électronique est
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