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

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

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

Suitability of high-pressure xenon as scintillator for gamma ray spectroscopy

In this paper we report the experimental study of high-pressure xenon used as a scintillator, in the context of developing a gamma ray detector. We measure a light yield near 2 photoelectrons per keV for xenon at 40 bar. Together with the light yield, we also measured an energy resolution of ~9% (FWHM) at 662 keV, dominated by the statistical fluctuations in the number of photoelectrons.Comment: 15 pages, 11 figure

First operation and performance of a 200 lt double phase LAr LEM-TPC with a 40x76 cm^2 readout

In this paper we describe the design, construction, and operation of a first large area double-phase liquid argon Large Electron Multiplier Time Projection Chamber (LAr LEM-TPC). The detector has a maximum drift length of 60 cm and the readout consists of a $40\times 76$ cm$^2$ LEM and 2D projective anode to multiply and collect drifting charges. Scintillation light is detected by means of cryogenic PMTs positioned below the cathode. To record both charge and light signals, we have developed a compact acquisition system, which is scalable up to ton-scale detectors with thousands of charge readout channels. The acquisition system, as well as the design and the performance of custom-made charge sensitive preamplifiers, are described. The complete experimental setup has been operated for a first time during a period of four weeks at CERN in the cryostat of the ArDM experiment, which was equipped with liquid and gas argon purification systems. The detector, exposed to cosmic rays, recorded events with a single-channel signal-to-noise ratio in excess of 30 for minimum ionising particles. Cosmic muon tracks and their $\delta$-rays were used to assess the performance of the detector, and to estimate the liquid argon purity and the gain at different amplification fields.Comment: 23 pages, 21 figure

Effects of High Charge Densities in Multi-GEM Detectors

A comprehensive study, supported by systematic measurements and numerical computations, of the intrinsic limits of multi-GEM detectors when exposed to very high particle fluxes or operated at very large gains is presented. The observed variations of the gain, of the ion back-flow, and of the pulse height spectra are explained in terms of the effects of the spatial distribution of positive ions and their movement throughout the amplification structure. The intrinsic dynamic character of the processes involved imposes the use of a non-standard simulation tool for the interpretation of the measurements. Computations done with a Finite Element Analysis software reproduce the observed behaviour of the detector. The impact of this detailed description of the detector in extreme conditions is multiple: it clarifies some detector behaviours already observed, it helps in defining intrinsic limits of the GEM technology, and it suggests ways to extend them.Comment: 5 pages, 6 figures, 2015 IEEE Nuclear Science Symposiu