Composés conjugués organophosphorés à coeur phosphole (applications pour l'électronique plastique)

Le développement des matériaux moléculaires connaît aujourd hui un essor considérable et leur intégration dans des dispositifs électroniques permet de concevoir de nouveaux produits très attractifs. Les travaux décrits ici portent sur la préparation et la caractérisation de composés organophosphorés intégrant un ou plusieurs motifs phospholes d une part, et sur leur utilisation dans des applications électroniques et optoélectroniques d autre part. Ce manuscrit est divisé en trois grandes parties. Le premier chapitre porte sur l utilisation des phospholes au sein de diodes électroluminescentes organiques. Dans une deuxième partie, ces composés ont été utilisés comme dopant de diodes blanches électroluminescentes organiques. Enfin, une nouvelle application a été visée: les transistors organiques à effet de champ.Development of molecular materials is receiving a great deal of attention. Their integration in electronics envisions the conception of very attractive products. The work presented here focuses on the preparation and characterization of organophosphorous compounds incorporating one or more phospholes moieties on one hand and on their use in electronic and optoelectronic applications on the other hand. This manuscript is divided into three main parts. The first chapter deals with the use of phospholes inside organic light-emitting diodes. In a second part, these compounds were used as a matrix dopant in white organic electroluminescent diodes. Finally, in the last chapter, new properties were highlighted and enabled us to tackle a new application for phospholes: the organic transistors.RENNES1-BU Sciences Philo (352382102) / SudocSudocFranceF

Toward Functional π-Conjugated Organophosphorus Materials: Design of Phosphole-Based Oligomers for Electroluminescent Devices

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C7 and C9 carbon-rich bridges in diruthenium systems: synthesis, spectroscopic, and theoretical investigations of different oxidation States.

International audienceTwo methodologies of C-C bond formation to achieve organometallic complexes with 7 or 9 conjugated carbon atoms are described. A C7 annelated trans-[Cl(dppe)2Ru=C=C=C-CH=C(CH2)-C[triple bond]C-Ru(dppe)2Cl][X] (X = PF6, OTf) complex is obtained from the diyne trans-[Cl(dppe)2Ru-(C[triple bond]C)2-R] (R = H, SiMe3) in the presence of [FeCp2][PF6] or HOTf, and C7 or C9 complexes trans-[Cl(dppe)2Ru-(C[triple bond]C)n-C(CH3)=C(R1)-C(R2)=C=C=Ru(dppe)2Cl][X] (n = 1, 2; R1 = Me, Ph, R2 = H, Me; X = BF4, OTf) are formed in the presence of a polyyne trans-[Cl(dppe)2Ru-(C[triple bond]C)n-R] (n = 2, 3; R = H, SiMe3) with a ruthenium allenylidene trans-[Cl(dppe)2Ru=C=C=C(CH2R1)R2][X]. These reactions proceed under mild conditions and involve cumulenic intermediates [M+]=(C=)nCHR (n = 3, 5), including a hexapentaenylidene. A combination of chemical, electrochemical, spectroscopic (UV-vis, IR, NIR, EPR), and theoretical (DFT) techniques is used to show the influence of the nature and conformation of the bridge on the properties of the complexes and to give a picture of the electron delocalization in the reduced and oxidized states. These studies demonstrate that the C7 bridging ligand spanning the metal centers by almost 12 angstroms is implicated in both redox processes and serves as a molecular wire to convey the unpaired electron with no tendency for spin localization on one of the halves of the molecules. The reactivity of the C7 complexes toward protonation and deprotonation led to original bis(acetylides), vinylidene-allenylidene, or carbyne-vinylidene species such as trans-[Cl(dppe)2Ru[triple bond]C-CH=C(CH3)-CH=C(CH3)-HC=C=Ru(dppe)2Cl][BF4]3