Halogen bonding stabilizes a cis-azobenzene derivative in the solid state: A crystallographic study

Crystals of trans- and cis-isomers of a fluorinated azobenzene derivative have been prepared and characterized by single-crystal X-ray diffraction. The presence of F atoms on the aromatic core of the azobenzene increases the lifetime of the metastable cis-isomer, allowing single crystals of the cis-azobenzene to be grown. Structural analysis on the cis-azobenzene, complemented with density functional theory calculations, highlights the active role of the halogen-bond contact (N...I synthon) in promoting the stabilization of the cis-isomer. The presence of a long aliphatic chain on the azobenzene unit induces a phase segregation that stabilizes the molecular arrangement for both the trans- and cis-isomers. Due to the rarity of cis-azobenzene crystal structures in the literature, our paper makes a step towards understanding the role of non-covalent interactions in driving the packing of metastable azobenzene isomers. This is expected to be important in the future rational design of solid-state, photoresponsive materials based on halogen bonding. We show by single-crystal X-ray diffraction studies and computational analysis that halogen bonding can stabilize a metastable cis-azobenzene derivative in the solid state

Efficient light-induced phase transitions in halogen-bonded liquid crystals

Here, we present a new family of light-responsive, fluorinated supramolecular liquid crystals (LCs) showing efficient and reversible light-induced LC-to-isotropic phase transitions. Our materials design is based on fluorinated azobenzenes, where the fluorination serves to strengthen the noncovalent interaction with bond-accepting stilbazole molecules, and increase the lifetime of the cis-form of the azobenzene units. The halogen-bonded LCs were characterized by means of X-ray diffraction, hot-stage polarized optical microscopy, and differential scanning calorimetry. Simultaneous analysis of light-induced changes in birefringence, absorption, and optical scattering allowed us to estimate that <4% of the mesogenic units in the cis-form suffices to trigger the full LC-to-isotropic phase transition. We also report a light-induced and reversible crystal-to-isotropic phase transition, which has not been previously observed in supramolecular complexes. In addition to fundamental understanding of light-responsive supramolecular complexes, we foresee this study to be important in the development of bistable photonic devices and supramolecular actuators

Coordination networks incorporating halogen-bond donor sites and azobenzene groups

Two Zn coordination networks, [Zn(1)(Py)2]2(2-propanol)n (3) and [Zn(1)2(Bipy)2](DMF)2n (4), incorporating halogen-bond (XB) donor sites and azobenzene groups have been synthesized and fully characterized. Obtaining 3 and 4 confirms that it is possible to use a ligand wherein its coordination bond acceptor sites and XB donor sites are on the same molecular scaffold (i.e., an aromatic ring) without interfering with each other. We demonstrate that XBs play a fundamental role in the architectures and properties of the obtained coordination networks. In 3, XBs promote the formation of 2D supramolecular layers, which, by overlapping each other, allow the incorporation of 2-propanol as a guest molecule. In 4, XBs support the connection of the layers and are essential to firmly pin DMF solvent molecules through I⋯O contacts, thus increasing the stability of the solvated systems

Reversible Graphene decoupling by NaCl photo-dissociation

We describe the reversible intercalation of Na under graphene on Ir(111) by photo-dissociation of a previously adsorbed NaCl overlayer. After room temperature evaporation, NaCl adsorbs on top of graphene forming a bilayer. With a combination of electron diffraction and photoemission techniques we demonstrate that the NaCl overlayer dissociates upon a short exposure to an X-ray beam. As a result, chlorine desorbs while sodium intercalates under the graphene, inducing an electronic decoupling from the underlying metal. Low energy electron diffraction shows the disappearance of the moir\'e pattern when Na intercalates between graphene and iridium. Analysis of the Na 2p core-level by X-ray photoelectron spectroscopy shows a chemical change from NaCl to metallic buried Na at the graphene/Ir interface. The intercalation-decoupling process leads to a n-doped graphene due to the charge transfer from the Na, as revealed by constant energy angle resolved X-ray photoemission maps. Moreover, the process is reversible by a mild annealing of the samples without damaging the graphene

Fermi surface instabilities in CeRh2Si2 at high magnetic field and pressure

We present thermoelectric power (TEP) studies under pressure and high magnetic field in the antiferromagnet CeRh2Si2 at low temperature. Under magnetic field, large quantum oscillations are observed in the TEP, S(H), in the antiferromagnetic phase. They suddenly disappear when entering in the polarized paramagnetic (PPM) state at Hc pointing out an important reconstruction of the Fermi surface (FS). Under pressure, S/T increases strongly of at low temperature near the critical pressure Pc, where the AF order is suppressed, implying the interplay of a FS change and low energy excitations driven by spin and valence fluctuations. The difference between the TEP signal in the PPM state above Hc and in the paramagnetic state (PM) above Pc can be explained by different FS. Band structure calculations at P = 0 stress that in the AF phase the 4f contribution at the Fermi level (EF) is weak while it is the main contribution in the PM domain. By analogy to previous work on CeRu2Si2, in the PPM phase of CeRh2Si2 the 4f contribution at EF will drop.Comment: 10 pages, 13 figure

Experimental Analysis of a Flat Plate Solar Collector with Integrated Latent Heat Thermal Storage

In the present paper, an experimental analysis of a solar water heating collector with an integrated latent heat storage unit is presented. With the purpose to determine the performance of a device on a lab scale, but with commercial features, a flat plate solar collector with phase change material (PCM) containers under the absorber plate was constructed and tested. PCM used was a commercial semi-refined light paraffin with a melting point of 60°C. Tests were carried out in outdoor conditions from October 2016 to March 2017 starting at 7:00 AM until the collector does not transfer heat to the water after sunset. Performance variables as water inlet temperature, outlet temperature, mass flow and solar radiation were measured in order to determine a useful heat and the collector efficiency. Furthermore, operating temperatures of the glass cover, air gap, absorber plate, and PCM containers are presented. Other external variables as ambient temperature, humidity and wind speed were measured with a weather station located next to the collector. The developed prototype reached an average thermal efficiency of 24.11% and a maximum outlet temperature of 50°C. Results indicate that the absorber plate reached the PCM melting point in few cases, this suggests that the use of a PCM with a lower melting point could be a potential strategy to increase thermal storage. A thermal analysis and conclusions of the device performance are discussed

Insulinoma : a propósito de un caso clínico

Se describe un caso de insulinoma en un perro. La presentación clínica inicial, algo oscura, permite realizar un protocolo diagnóstico diferencial primero del síndrome de debilidad, luego de hipoglucemia, y finalmente confirmar el insulinoma por las correspondientes pruebas endocrinológicas, incluido el test de la fructosamina, y visualización de nódulos característicos en páncreas gracias a la exploración ecográfica.A case of insulinoma in the dog is described. Due to the initially unclear clinical picture, a differential diagnosis of weakness is carried out at first, of hypoglycemia later, and after the endocrinologycal tests (including the fructosamine test) and ultrasonographic examination (visualizing characteristic pancreatic nodules) a final diagnosis of insulinoma is made

Hierarchical Self-Assembly of Halogen-Bonded Block Copolymer Complexes into Upright Cylindrical Domains

Self-assembly of block copolymers into well-defined, ordered arrangements of chemically distinct domains is a reliable strategy for preparing tailored nanostructures. Microphase separation results from the system, minimizing repulsive interactions between dissimilar blocks and maximizing attractive interactions between similar blocks. Supramolecular methods have also achieved this separation by introducing small-molecule additives binding specifically to one block by noncovalent interactions. Here, we use halogen bonding as a supramolecular tool that directs the hierarchical self-assembly of low-molecular-weight perfluorinated molecules and diblock copolymers. Microphase separation results in a lamellar-within-cylindrical arrangement and promotes upright cylindrical alignment in films upon rapid casting and without further annealing. Such cylindrical domains with internal lamellar self-assemblies can be cleaved by solvent treatment of bulk films, resulting in separated and segmented cylindrical micelles stabilized by halogen-bond-based supramolecular crosslinks. These features, alongside the reversible nature of halogen bonding, provide a robust modular approach for nanofabricatio

Structural and magnetic behavior of the S=2 layered ferromagnet CsMnF4 under hydrostatic pressure

Under the terms of the Creative Commons Attribution License 3.0 (CC-BY).Pressure-induced transformations in the structural and magnetic properties of CsMnF4 are reported. This behavior is analyzed in the framework of magnetostructural correlations within the layered perovskite AMnF4 (A=Cs,Rb,K) series by using magnetic susceptibility and synchrotron x-ray powder-diffraction techniques as a function of temperature and hydrostatic pressure.We would like to thank C.I.C.Y.T. for Grants Nos. MAT94-43 and MAT91-681, U.K. Science Ez. Engineering Research Council for providing Synchrotron Radiation beam time under the E.C. Large Scale Facilities Programme, CNPq and the Programa de Cooperacion Cientifica con Iberoamerica.Peer Reviewe