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The SIRIUS beamline of Synchrotron SOLEIL is dedicated to X-ray scattering and spectroscopy of surfaces and interfaces, covering the tender to mid-hard X-ray range (1.1-13 keV). The beamline has hosted a wide range of experiments in the field of soft interfaces and beyond, providing various grazing-incidence techniques such as diffraction and wide-angle scattering (GIXD/GIWAXS), small-angle scattering (GISAXS) and X-ray fluorescence in total reflection (TXRF). SIRIUS also offers specific sample environments tailored for in situ complementary experiments on solid and liquid surfaces. Recently, the beamline has added compound refractive lenses associated with a transfocator, allowing for the X-ray beam to be focused down to 10 μm × 10 μm while maintaining a reasonable flux on the sample. This new feature opens up new possibilities for faster GIXD measurements at the liquid-air interface and for measurements on samples with narrow geometries. [ABSTRACT FROM AUTHOR]

We show that through the introduction of short dimethylsiloxane chains, it was possible to suppress the crystalline state of CBP in favor of various types of organization, transitioning from a soft crystal to a fluid liquid crystal mesophase, then to a liquid state. Characterized by X-ray scattering, all organizations reveal a similar layered configuration in which layers of edge-on lying CBP cores alternate with siloxane. The difference between all CBP organizations essentially lay on the regularity of the molecular packing that modulates the interactions of neighboring conjugated cores. As a result, the materials show quite different thin film absorption and emission properties, which could be correlated to the features of the chemical architectures and the molecular organizations. [ABSTRACT FROM AUTHOR]

Over the past decade, halogenated semiconducting polymers have attracted considerable interest due to their outstanding optoelectronic properties. Thus, in most of today's organic photovoltaic devices benchmark organic semiconductors are halogenated materials, either electron donor polymers or non‐fullerene acceptor (NFA) small molecules. However, the nature and position of the substituted halogen atoms in halogenated semiconducting polymers impact, through self‐assembly modification, their optoelectronic properties in a way that is difficult to predict. Yet, the solid‐state self‐assembling of these materials has been shown to be a key parameter toward high charge transport properties and photovoltaic efficiencies. In this context, there is still a need to develop analytical methods that will enable an atomic‐scale structural characterization of these materials as a function of the halogenation. In this study, the solid‐state nuclear magnetic resonance (NMR) under magic angle spinning (MAS) is explored as a tool to investigate the local structure and supramolecular organization of a series of conjugated polymers, specially designed for this study. Through a comprehensive study using complementary techniques, including MAS–NMR, small and wide‐angle X‐ray scattering, and molecular modeling investigations, the molecular conformation of these polymers in relation to their chemical composition, is successfully determined. [ABSTRACT FROM AUTHOR]

Featured Application: The study was conducted as fundamental research aiming new advanced materials characterized envisaging applications of non-enzymatic electrochemical sensing. The synthesis and structural characterization of a new liquid crystalline coordination complex based on pentacoordinated Zn(II) metal centre with the coordination fulfilled by the tridentate chelating N^N^N 2,2′;6′,2″-terpyridine ligand and two monoanionic gallates decorated with several long alkyl chains is described. The mesomorphic properties were accurately investigated by small- and wide-angle X-ray scattering studies. Despite the bulky coordination around the metal centre, the complex self-organizes into a smectic phase and, based on the structural and geometrical parameters, a model for the supramolecular organization in the liquid crystalline phase is proposed. Electrochemical investigations showed the importance of the molecular structure of the coordination complex in enhancing its aqueous sensing capacities: the bulky organic ligands form an organic shell separating the metal centres and favouring the redox system through their reduction followed by stripping. [ABSTRACT FROM AUTHOR]

The synthesis of the first mesogenic donor‐acceptor polyoxometalate (POM)‐based hybrid is herein described. The structural and electronic properties of the hybrid compound were evaluated through combination of small‐ and wide‐angle X‐ray scattering, optical microscopy, electrochemistry and photoluminescence. In the solid state, the compound behaves as a birefringent solid, displaying a lamellar organization in which double‐layers of POMs and bis(thiophene)thienothiophene organic donors alternate regularly. Noticeably, the sub‐unit organizations in the composite are similar to that observed for the individual POM and organic donor precursors. Photophysical studies show that in the hybrid, the fluorescence of the organic donor unit is considerably quenched both in solution and in the solid state, which is attributed to occurrence of intramolecular charge‐separated state. [ABSTRACT FROM AUTHOR]

Blue–green luminescent terpyridine‐containing PtII and ZnII complexes are reported. Equipped with lipophilic gallate units, which act as monodentate ancillary coordinating ligands and/or as anions, they display low‐temperature mesomorphic properties (lamello‐columnar and hexagonal mesophases for PtII and ZnII complexes, respectively). The mesomorphic properties were investigated by polarised optical microscopy, differential scanning calorimetry, thermogravimetric analysis and X‐ray scattering of bulk materials and oriented thin films. The model of self‐assembly into the lamello‐columnar phase of the PtII complex has been described in detail. The optical properties of the complexes were investigated in the liquid and condensed liquid crystalline states, highlighting the delicate balance between the role of the metal in determining the type of excited state responsible for the emission, and the role of the ancillary ligand in driving intermolecular interactions for proper mesophase formation. [ABSTRACT FROM AUTHOR]

Mesomorphic properties and structures of two mix-substituted lipophilic phthalocyanine derivatives of the A3B type, with a different ratio of electron-donating (hexadecyloxy-) and electron-withdrawing (Cl-) substituents on the isoindol fragments ‘A’ and ‘B’, correspondingly, were studied by polarising optical microscopy, differential scanning calorimetry and small-angle X-ray scattering. Both compounds display columnar mesophases, and the type of organisation of the columns in the mesomorphic state was found to strongly depend on the number of peripheral chlorine substituents in the molecule. The di-chloro-substituted phthalocyanine forms a solid pasty lamellar phase at room temperature, which on heating undergoes successive transitions to two large-lattice columnar mesophases (2D-Colh and 3D-MCol) arising from the aggregation of several phthalocyanine-containing piles. On the contrary, aggregation of columns does not occur for the tetra-chloro-substituted phthalocyanine, which forms a nematic columnar mesophase of single phthalocyanine piles (1D-NCol). While the di-chloro-compound partly crystallises on cooling, the nematic phase of the tetra-chloro-compound freezes at room temperature. The reasons for this different self-organisation behaviour are not yet fully understood, but some hints may be deduced from the proposed supramolecular models. [ABSTRACT FROM AUTHOR]

A new series of neutral protomesogenic EuIII tris(β-diketonate) adducts with different Lewis bases have been synthesized. Only one of the complexes is liquid-crystalline and displays smectic A and nematic mesomorphism over a broad temperature range. Quantum-chemistry and small-angle X-ray scattering methods have permitted the evaluation of the influence of the structure of the Lewis base on the anisometry of EuIII adduct molecules and their subsequent supramolecular organization. The structural features of the presented compounds allow the creation of vitrified optically isotropic and self-organized films with effective red luminescence. The luminescence spectra of aligned thin films of a liquid-crystalline EuIII complex are also described. [ABSTRACT FROM AUTHOR]

Large electron injection barriers and electrode degradation are serious issues that need to be overcome to obtain n-channel operation in field-effect transistors with an organic-inorganic layered perovskite (C6H5C2H4NH3)2SnI4 semiconductor. By employing low-work-function Al source/drain electrodes and by inserting C60 layers between the perovskite semiconductor and the Al electrodes to reduce the injection barrier and to suppress the electrode degradation, we demonstrate n-channel perovskite transistors with electron mobilities of up to 2.1 cm2/V s, the highest value ever reported in spin-coated perovskite transistors. The n-channel transport properties of these transistors are relatively stable in vacuum but are very sensitive to oxygen, which works as electron traps in perovskite and C60 layers. In addition, grazing-incidence X-ray scattering and thermally stimulated current measurements revealed that crystallite size and electron traps largely affect the n-channel transport properties. [ABSTRACT FROM AUTHOR]

Embedding nanoparticles (NPs) with organic shells is a way to control their aggregation behavior. Using polymers allows reaching relatively high shell thicknesses but suffers from the difficulty of obtaining regular hybrid objects at gram scale. Here, we describe a three-step synthesis in which multi-gram NP batches are first obtained by thermal decomposition, prior to their covalent grafting by an atom transfer radical polymerization (ATRP) initiator and to the controlled growing of the polymer shell. Specifically, non-aggregated iron oxide NPs with a core principally composed of γ-Fe2O3 (maghemite) and either polystyrene (PS) or polymethyl methacrylate (PMMA) shell were elaborated. The oxide cores of about 13 nm diameter were characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). After the polymerization, the overall diameter reached 60 nm, as shown by small-angle neutron scattering (SANS). The behavior in solution as well as rheological properties in the molten state of the polymeric shell resemble those of star polymers. Strategies to further improve the screening of NP cores with the polymer shells are discussed. [ABSTRACT FROM AUTHOR]