Influence of the Side Chain Structure on the Electronic Structure and Self-Organization Properties of Low Band Gap Polymers

The properties of low band gap polymers in devices such as solar cells are strongly influenced by their morphology and ability of self-organization in thin films and interface properties. We study the influence of alkyl and alkoxy side chain position for four conjugated, alternating oligothiophene-benzothiadiazole copolymers on the molecular orientation in thin films and electronic interface properties using photoemission, X-ray absorption spectroscopy (XAS) at the sulfur K edge, and polarization modulation-infrared reflection–absorption spectroscopy (PMIRRAS). The interface charge transfer (ICT) model is used to explain interface properties of the polymers on substrates with different work functions. We find that the position of the side chains has a significant influence on the orientation and thus on self-organization properties of the polymers in thin films, whereas the electronic structure is less affected. The preferred molecular orientation is further affected by annealing, leading to a higher degree of ordering. Results from complementary methods with different surface sensitivities (XAS in total electron yield and fluorescence mode and PMIRRAS) are discussed

Spin crossover in Fe(triazole)–Pt nanoparticle self-assembly structured at the sub-5 nm scale

A main goal of molecular electronics is to relate the performance of devices to the structure and electronic state of molecules. Among the variety of possibilities that organic, organometallic and coordination chemistries offer to tune the energy levels of molecular components, spin crossover phenomenon is a perfect candidate for elaboration of molecular switches. The reorganization of the electronic state population of the molecules associated to the spin crossover can indeed lead to a significant change in conductivity. However, molecular spin crossover is very sensitive to the environment and can disappear once the molecules are integrated into devices. Here, we show that the association of ultra-small 1.2 nm platinum nanoparticles with FeII triazole-based spin crossover coordination polymers leads to self-assemblies, extremely well organized at the sub-3 nm scale. The quasi-perfect alignment of nanoparticles observed by transmission electron microscopy, in addition to specific signature in infrared spectroscopy, demonstrates the coordination of the long-chain molecules with the nanoparticles. Spin crossover is confirmed in such assemblies by X-ray absorption spectroscopic measurements and shows unambiguous characteristics both in magnetic and charge transport measurements. Coordinating polymers are therefore ideal candidates for the elaboration of robust, well-organized, hybrid self-assemblies with metallic nanoparticles, while maintaining sensitive functional properties, such as spin crossover

The origin of the high electrochemical activity of pseudo-amorphous iridium oxides

The origins of the superior catalytic activity of poorly crystallized Ir-based oxide material for the OER in acid is still under debate. Here, authors synthesize porous IrMo oxides to deconvolute the effect of Ir oxidation state from short-range ordering and show the latter to be a key factor

Microspectroscopy reveals dust-derived apatite grains in acidic, highly-weathered Hawaiian soils

Dust deposition is an important source of phosphorus (P) to many ecosystems. However, there is little evidence of dust-derived P-containing minerals in soils. Here we studied P forms along a well-described climatic gradient on Hawaii, which is also a dust deposition gradient. Soil mineralogy and soil P forms from six sites along the climatic gradient were analyzed with bulk (X-ray diffraction and P K-edge X-ray absorption near edge structure) and microscale (X-ray fluorescence, P K-edge X-ray absorption near edge structure, and Raman) analysis methods. In the wettest soils, apatite grains ranging from 5 to 30 µm in size were co-located at the micro-scale with quartz, a known continental dust indicator suggesting recent atmospheric deposition. In addition to co-location with quartz, further evidence of dust-derived P included backward trajectory modeling indicating that dust particles could be brought to Hawaii from the major global dust-loading areas in central Asia and northern Africa. Although it is not certain whether the individual observed apatite grains were derived from long-distance transport of dust, or from local dust sources such as volcanic ash or windblown fertilizer, these observations offer direct evidence that P-containing minerals have reached surface layers of highly-weathered grassland soils through atmospheric deposition

Activation d'une molécule d'eau coordonnée au manganèse : quatre études de cas.

The daunting energy consumption of western societies calls for the development of renewable energies. Among them, hydrogen stands as a major candidate. The cleanest way of producing hydrogen is water electro- or photolysis. This reaction is carried out in natural photosynthesis by a manganese-oxo cluster, the functioning of which remains unknown. Insight into this mechanism would greatly help the search for low-cost water splitting catalysts. Our contribution to this field is the understanding of the fundamental processes that govern the activation of water by manganese complexes. This manuscript describes our attempts to generate electrochemically mononuclear manganese(IV) complexes bearing a fully deprotonated water molecule (oxo ligand). We have studied four different cases, which reflect different possible coordination spheres capable of stabilizing such species. In the first chapter, we will give a brief overview of the present energetic challenges faced by western societies. In the second chapter, we will present general considerations about manganese chemistry and a descprition of the structure and functioning of the water oxidizing enzyme. We will also describe the basic requirements for the splitting of water and present the goals of our work. In the third chapter, we will present the synthesis of a new family of tetradentate ligands, together with the synthesis and full characterization of the corresponding nickel(II) complexes. The first results obtained with the manganese analogue will also be shown. Chapter four presents the formation and the full characterization of a mononuclear manganese(IV)-oxo complex, by electrochemical oxidation of a manganese(II)-aqua complex. We will present different pathways to generate this species and show which intermediates are involved in this 2 e-, 2 H+ reaction. Chapter five describes the formation of a mononuclear manganese(IV) complex, by electrochemical oxidation of a manganese(III)-hydroxo complex. The manganese(IV) complex has not been fully characterized yet, but these results provide important information on the criteria for the formation of mononuclear versus dinuclear complexes. Chapter six presents the synthesis of a new binucleating ligand for the preparation of face-to-face dinuclear manganese complexes.Les conséquences économiques, politiques et environnementales de la consommation énergétique galopante de nos sociétés nécessitent le développement d'énergies renouvelables. Le dihydrogène est un des principaux candidats à ce poste. Sa production par électro- ou photolyse de l'eau est réalisée par des catalyseurs métalliques. Dans le processus de la photosynthèse, cette réaction est réalisée par un agrégat d'ions manganèses liés par des ponts oxo, selon un mécanisme qui reste inconnu. Le développement de nouveaux catalyseurs de coût plus faible nécessite la compréhension des mécanismes fondamentaux de la réaction d'oxydation de l'eau. Notre travail de thèse a consisté à étudier les étapes élémentaires de cette réaction, à savoir, l'activation d'une molécule d'eau par des complexes de manganèse. Nous avons étudié pour cela la formation par voie électrochimique de complexes mononucléaires manganèse(IV) et (V)-oxo. Le premier chapitre traite de la problématique environnementale et énergétique actuelle. Le second chapitre décrit les éléments fondamentaux de la chimie du manganèse, ainsi que la structure et le fonctionnement de l'enzyme responsable de l'oxydation de l'eau. Une approche générale de la catalyse artificielle d'oxydation de l'eau est également présentée, ainsi que les objectifs de nos travaux. Le chapitre trois présente la synthèse et la caractérisation d'une nouvelle famille de ligands tétradente et des complexes de nickel(II) et de manganèse(III) correspondant. La préparation électrochimique de complexes de nickel(III) et manganèse(V) est présentée. Le chapitre quatre décrit la préparation d'un complexe mononucléaire manganèse(IV)- oxo par oxydation électrochimique d'un complexe manganèse(II)-aqua. Le complexe de manganèse(IV), ainsi que certains intermédiaires de manganèse(III) ont été caractérisés par différentes techniques spectroscopiques. Le chapitre cinq présente la synthèse d'une famille de ligands pentadentes et des complexes de manganèse(II) et (III) correspondant. La formation électrochimique de deux complexes de manganèse(IV) mononucléaire et (III/IV) dinucléaire nous renseigne sur les critères régissant la nucléarité au sein d'une même famille de ligands. Le chapitre six présente la synthèse d'un ligand possédant une double cavité, pour l'élaboration de complexes dinucléaires de manganèse en face-à-face

Activation d'une molécule d'eau coordonnée au manganèse (quatre études de cas)

Le travail décrit dans ce manuscrit consiste en la synthèse de complexes mononucléaries de manganèse (IV) à ligand oxo terminal par voie électrochimique. Les complexes de manganèse (II) ou (III) précurseurs sont synthétisés à partir de ligands tétra ou pentadentes monotopiques, azotés et oxygénés. Ces complexes ainsi que leurs analogues au degré d'oxydation +IV préparés par voie électrochimique, sont analysés par voltamétrie cyclique, spectroscopies UV-Visible, RPE et d'absorptions des rayons X. Des calculs de type DFT ont également été réalisés sur un des complexes de manganèse (IV). Ces travaux s'insèrent dans le champ de la photosynthèse artificielle, avec pour but d'améliorer la compréhension du mécanisme photosynthétique d'oxydation de l'eau.The present thesis deals about the formation by electrochemical oxidation of mononuclear manganese(IV) complexes, bearing a terminal oxo ligand. The manganese(II) or (III) precursor complexes has been prepared with tetradentate or pentadentate monotopic ligands. These complexes, as well as their +IV oxidation state counterparts, has been thoroughly studied by cyclic voltametry, UV-visible, EPR and X-ray absorption spectroscopies. DFT calculations has also been performed on one of these complexes. The results obtained help advancing the artificial photsynthesis research field, and bring synthetic clues to the functioning of the natural photosynthetic water oxidation process.ORSAY-PARIS 11-BU Sciences (914712101) / SudocSudocFranceF

A millisecond passive micromixer with low flow rate, low sample consumption and easy fabrication

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