Remarkable emissions in diprotonated 2,2′:6′,2″‐terpyridine derivatives

A series of new metal‐free blue emission compounds, i.e., diprotonated terpyH₂ClPF₆ ( 1 ), tterpyH₂ClPF₆ ( 2 ), ClterpyH₂ClPF₆ ( 3 ), and BterpyH₂(PF₆)₂ ( 4 ), were prepared and characterized by electrospray ionization mass spectrometry, UV–vis spectroscopy, and cyclic voltammetry (CV). Abbreviations used are terpy = 2,2′:6′,2″‐terpyridine, tterpy = 4′‐(4‐tolyl)‐2,2′:6′,2″‐terpyridine, Clterpy = 4′‐chloro‐2,2′:6′,2″‐terpyridine, and Bterpy = 4,4′,4″‐tert‐butyl‐2,2′:6′,2″‐terpyridine. The X‐ray crystal structures of the three new compounds 1, 2, and 4 were determined. Both protonated pyridine rings of the terpyridine derivatives are hydrogen bonded intermolecularly to the adjacent Cl^? ion in compounds 1 , 2, and 3 . The π–π* absorption bands in the UV region for 1, 2, 3, and 4 in acetonitrile were red‐shifted relative to those of the corresponding neutral compounds. All the compounds exhibited stronger emissions (around 400 nm) than their neutral counterparts. All the CVs for the diprotonated species, terpyH, tterpyH, ClterpyH, and BterpyH, showed the first reduction waves around ?0.6 V, which were more positive than those of the neutral ones. Density functional theory was applied to interpret the remarkable differences in the interaction of the Cl^? ion. The attachment of two protons to the two terminal Bterpy nitrogens in 4 elicits remarkable characteristics. Both positive charges on the nitrogens are delocalized over the conjugated pyridine systems and the tertiary carbonium ions are stabilized to lead to stronger emission (Φ = 0.35) than the corresponding neutral Bterpy (Φ = 0.045). CCDC 732045–732047 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif Copyright © 2010 John Wiley & Sons, Ltd.     

The key Cl− ligand for metal‐to‐ligand charge transfer in mononuclear terpyridine ruthenium(II) and binuclear ruthenium(II) tetrapyridylpyrazine complexes

Electronic structures of binuclear ruthenium complexes [Ru₂(terpy)₂(tppz)]⁴⁺ ( 1A ) and [Ru₂Cl₂(L)₂(tppz)]²⁺ {L = bpy ( 2A ), phen ( 3A ), and dpphen ( 4A )} were studied by density functional theory calculations. Abbreviations of the ligands (Ls) are bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline, dpphen = 4,7‐diphenyl‐1,10‐phenanthroline, terpy = 2,2′:6′,2″‐terpyridine, and tppz = tetrakis(2‐pyridyl)pyrazine. Their mononuclear reference complexes [Ru(terpy)₂]²⁺ ( 1B ) and [RuClL(terpy)]⁺ {L = bpy ( 2B ), phen ( 3B ), and dpphen ( 4B )} were also examined. Geometries of these mononuclear and binuclear Ru(II) complexes were fully optimized. Their geometric parameters are in good agreement with the experimental data. The binuclear complexes were characterized by electrospray ionization mass spectrometry, UV–Vis spectroscopy, and cyclic voltammograms. Hexafluorophosphate salts of binuclear ruthenium complexes of 3A and 4A were newly prepared. The crystal structure of binuclear complex 1A (PF₆)₄ was also determined. Orbital interactions were analyzed to characterize the metal‐to‐ligand charge‐transfer (MLCT) states in these complexes. The Cl^? ligand works to raise the orbital energy of the metal lone pair, which leads to the low MLCT state. Copyright © 2011 John Wiley & Sons, Ltd.     

Syntheses,X‐ray crystal structures,and emission properties of protonated tripyridyltriazines and their ruthenium(II) complexes

A series of metal‐free compounds, ie, planar triprotonated triazine, triazineH₃Cl(PF₆)₂ ( 1 ), planar triprotonated triazineH₃Br(PF₆)₂ ( 2 ), and nonplanar monoprotonated triazineHPF₆ ( 3 ), were prepared. Abbreviations used are triazine = tri‐2‐pyridyltriazine. Ruthenium complexes [RuCl(bpy)(L)](PF₆), [RuCl(bpy)(L)](PF₆)₂, and [Ru(L)₂](PF₆)₂ were also prepared, where bpy is 2,2′‐bipyridine and L's are triazine ( 4 ) and monoprotonated triazine ( 5 ), respectively. Ruthenium complexes [Ru(triazine)₂](PF₆)₂ ( 6 ) were also prepared and crystallized. The X‐ray crystal structures of the 3 compounds 1 , 2 , and 3 and the complex 6 were determined. They were also characterized by electrospray ionization mass spectrometry, UV‐vis spectroscopy, and density functional theory calculations.     

A three‐crystal spectrometer for high‐energy resolution fluorescence‐detected X‐ray absorption spectroscopy and X‐ray emission spectroscopy at SSRF

A Johann‐type spectrometer for the study of high‐energy resolution fluorescence‐detected X‐ray absorption spectroscopy, X‐ray emission spectroscopy and resonant inelastic X‐ray scattering has been developed at BL14W1 X‐ray absorption fine structure spectroscopy beamline of Shanghai Synchrotron Radiation Facility. The spectrometer consists of three crystal analyzers mounted on a vertical motion stage. The instrument is scanned vertically and covers the Bragg angle range of 71.5–88°. The energy resolution of the spectrometer ranges from sub‐eV to a few eV. The spectrometer has a solid angle of about 1.87 × 0^?3 of 4π sr, and the overall photons acquired by the detector could be 10⁵ counts per second for the standard sample. The performances of the spectrometer are illustrated by the three experiments that are difficult to perform with the conventional absorption or emission spectroscopy. Copyright © 2016 John Wiley & Sons, Ltd.     

Trifluoromethanesulfonamide: X‐ray single‐crystal determination and quantum chemical calculations

The X‐ray single‐crystal structure of 1,1,1‐trifluoromethanesulfonamide (triflamide) CF₃SO₂NH₂, which is the ancestor of a large family of its derivatives, has been determined. The crystal structure is composed of infinite layers with an interlayer distance of 3.4 Å. Geometry optimization at the Møller‐Plesset (MP2) and density functional theory (DFT) level showed the calculated bond distances to be, as a rule, longer than the experimental ones. A trial to simulate crystal packing effect on the geometrical parameters by calculating the dimer of triflamide in the gas phase failed – the starting X‐ray geometry of the ‘dimeric’ unit with one NH···O=S H‐bond – was optimized to the cyclic dimer with two H‐bonds. However, when the external (crystal) field effect was simulated using the polarizable continuum model, the experimental geometry of the ‘dimeric’ fragment was satisfactorily reproduced. Calculations of the heptamer cluster having the structure of the hexagon with six triflamide molecules in vertices and one in the middle nicely reproduce the X‐ray structure and brings the geometrical parameters closer to the experiment. Copyright © 2015 John Wiley & Sons, Ltd.     

Confocal full‐field X‐ray microscope for novel three‐dimensional X‐ray imaging

A confocal full‐field X‐ray microscope has been developed for use as a novel three‐dimensional X‐ray imaging method. The system consists of an X‐ray illuminating `sheet‐beam' whose beam shape is micrified only in one dimension, and an X‐ray full‐field microscope whose optical axis is normal to the illuminating sheet beam. An arbitral cross‐sectional region of the object is irradiated by the sheet‐beam, and secondary X‐ray emission such as fluorescent X‐rays from this region is imaged simultaneously using the full‐field microscope. This system enables a virtual sliced image of a specimen to be obtained as a two‐dimensional magnified image, and three‐dimensional observation is available only by a linear translation of the object along the optical axis of the full‐field microscope. A feasibility test has been carried out at beamline 37XU of SPring‐8. Observation of the three‐dimensional distribution of metallic inclusions in an artificial diamond was performed.     

Three green luminescent cadmium complexes containing 8-aminoquinoline ligands: Syntheses, crystal structures, emission spectra and DFT calculations

Three complexes, Cd(8-aminoql)₂×₂ (8-aminoql=8-aminoquinoline; X⁻=ClO₄⁻, SCN⁻, 1 and 2, respectively) and Cd(8-aminoql)(N₃)₂ (3), were synthesized and structurally characterized. For each complex, the Cd²⁺ ion exhibits distorted octahedral coordination geometry. Two 8-aminoquinoline molecules and two counter-anions are coordinated to the Cd²⁺ center to form a mononuclear species with two trans-ClO₄⁻ anions for 1, while two SCN⁻ anions adopt a cis-configuration for 2. The intermolecular H-bonding interactions between the -NH₂ groups and the O atom (1) and the S atom (2) result in the formation of a 2-D layered structure. In the crystal of 3, the N₃⁻ anions bridging the neighboring Cd(8-aminoql)²⁺ units form a 1-D coordination polymer. The three complexes emit green luminescence. The emission bands possess a broad asymmetric feature, which can be assigned to L′LCT transitions based on DFT and TDDFT calculations.     

Optimizing and characterizing grating efficiency for a soft X‐ray emission spectrometer

The efficiency of soft X‐ray diffraction gratings is studied using measurements and calculations based on the differential method with the S‐matrix propagation algorithm. New open‐source software is introduced for efficiency modelling that accounts for arbitrary groove profiles, such as those based on atomic force microscopy (AFM) measurements; the software also exploits multi‐core processors and high‐performance computing resources for faster calculations. Insights from these calculations, including a new principle of optimal incidence angle, are used to design a soft X‐ray emission spectrometer with high efficiency and high resolution for the REIXS beamline at the Canadian Light Source: a theoretical grating efficiency above 10% and resolving power E/ΔE > 2500 over the energy range from 100 eV to 1000 eV are achieved. The design also exploits an efficiency peak in the third diffraction order to provide a high‐resolution mode offering E/ΔE > 14000 at 280 eV, and E/ΔE > 10000 at 710 eV, with theoretical grating efficiencies from 2% to 5%. The manufactured gratings are characterized using AFM measurements of the grooves and diffractometer measurements of the efficiency as a function of wavelength. The measured and theoretical efficiency spectra are compared, and the discrepancies are explained by accounting for real‐world effects: groove geometry errors, oxidation and surface roughness. A curve‐fitting process is used to invert the calculations to predict grating parameters that match the calculated and measured efficiency spectra; the predicted blaze angles are found to agree closely with the AFM estimates, and a method of characterizing grating parameters that are difficult or impossible to measure directly is suggested.     

A miniature X‐ray emission spectrometer (miniXES) for high‐pressure studies in a diamond anvil cell

Core–shell X‐ray emission spectroscopy (XES) is a valuable complement to X‐ray absorption spectroscopy (XAS) techniques. However, XES in the hard X‐ray regime is much less frequently employed than XAS, often as a consequence of the relative scarcity of XES instrumentation having energy resolutions comparable with the relevant core‐hole lifetimes. To address this, a family of inexpensive and easily operated short‐working‐distance X‐ray emission spectrometers has been developed. The use of computer‐aided design and rapid prototype machining of plastics allows customization for various emission lines having energies from ～3 keV to ～10 keV. The specific instrument described here, based on a coarsely diced approximant of the Johansson optic, is intended to study volume collapse in Pr metal and compounds by observing the pressure dependence of the Pr Lα emission spectrum. The collection solid angle is ～50 msr, roughly equivalent to that of six traditional spherically bent crystal analyzers. The miniature X‐ray emission spectrometer (miniXES) methodology will help encourage the adoption and broad application of high‐resolution XES capabilities at hard X‐ray synchrotron facilities.     

Flexible X‐ray detector based on sliced lead iodide crystal

A promising flexible X‐ray detector based on inorganic semiconductor PbI₂ crystal is reported. The sliced crystals mechanically cleaved from an as‐grown PbI₂ crystal act as the absorber directly converting the impinging X‐ray photons to electron hole pairs. Due to the ductile feature of the PbI₂ crystal, the detector can be operated under a highly curved state with the strain on the top surface up to 1.03% and still maintaining effective detection performance. The stable photocurrent and fast response were obtained with the detector repeated bending to a strain of 1.03% for 100 cycles. This work presents an approach for developing efficient and cost‐effective PbI₂‐based flexible X‐ray detector.

     

L‐series X‐ray emission spectra of 3d‐metal compounds with various excitation conditions

L‐series emissions of manganese, iron, and zinc oxides were studied using electron beam excitation and highly brilliant synchrotron radiation excitation. We showed that manganese and iron oxides show different Lβ/Lα intensity ratio because of their oxidation states and excitation electron voltages. On the other hand, we could not get any L‐series emissions from those bulk samples when excited by normal incident high‐energy monochromatic X‐rays, while samples of thin films and samples excited by grazing incident monochromatic X‐rays showed clear emissions. It is suggested that the difference of Lβ/Lα intensity ratio due to the oxidized states mainly concerns with the Coster–Kronig transition ratio of the samples, while self‐absorption effects should also deeply contribute the ratio, considering the experimental results. Copyright © 2016 John Wiley & Sons, Ltd.     

Combined measurement of X‐ray photon correlation spectroscopy and diffracted X‐ray tracking using pink beam X‐rays

Combined X‐ray photon correlation spectroscopy (XPCS) and diffracted X‐ray tracking (DXT) measurements of carbon‐black nanocrystals embedded in styrene–butadiene rubber were performed. From the intensity fluctuation of speckle patterns in a small‐angle scattering region (XPCS), dynamical information relating to the translational motion can be obtained, and the rotational motion is observed through the changes in the positions of DXT diffraction spots. Graphitized carbon‐black nanocrystals in unvulcanized styrene–butadiene rubber showed an apparent discrepancy between their translational and rotational motions; this result seems to support a stress‐relaxation model for the origin of super‐diffusive particle motion that is widely observed in nanocolloidal systems. Combined measurements using these two techniques will give new insights into nanoscopic dynamics, and will be useful as a microrheology technique.     

Single‐crystal X‐ray diffraction and resonant X‐ray magnetic scattering at helium‐3 temperatures in high magnetic fields at beamline P09 at PETRA III

The resonant scattering and diffraction beamline P09 at PETRA III at DESY is equipped with a 14 T vertical field split‐pair magnet. A helium‐3 refrigerator is available that can be fitted inside the magnet's variable‐temperature insert. Here the results of a series of experiments aimed at determining the beam conditions permitting operations with the He‐3 insert are presented. By measuring the tetragonal‐to‐orthorhombic phase transition occurring at 2.1 K in the Jahn–Teller compound TmVO₄, it is found that the photon flux at P09 must be attenuated down to 1.5 × 10⁹ photons s^?1 for the sample to remain at temperatures below 800 mK. Despite such a reduction of the incident flux and the subsequent use of a Cu(111) analyzer, the resonant X‐ray magnetic scattering signal at the Tm L_III absorption edge associated with the spin‐density wave in TmNi₂B₂C below 1.5 K is intense enough to permit a complete study in magnetic field and at sub‐Kelvin temperatures to be carried out.     

Correlation of Electron Beams and Hard X‐ray Emissions in ISTTOK Tokamak

The paper reports on experimental studies of electron beams in the ISTTOK tokamak, those were performed by means of an improved four‐channel detector. The Cherenkov‐type detector measuring head was equipped with four radiators made of two types of alumina‐nitrate (AlN) poly‐crystals: machinable and translucent ones, both of 10 mm in diameter and 2.5 mm in thickness. The movable support that enabled the whole detectors to be placed inside the tokamak vacuum chamber, at chosen positions along the ISTTOK minor radius. Since the electron energy distribution is one of the most important characteristics of tokamak plasmas, the main aim of the study was to perform estimations of an energy spectrum of the recorded electrons. For this purpose the radiators were coated with molybdenum (Mo) layers of different thickness. The technique based on the use of Cherenkov‐type detectors enabled the detection of fast electrons (of energy above 66 keV) and determination of their spatial and temporal characteristics in the ISTTOK experiment. Measurements of hard X‐rays (HXR), which were emitted during ISTTOK discharges, have also been performed. Particular attention was paid to the correlation measurements of HXR pulses with run‐away electron beams. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Pressure study of monoclinic ReO2 up to 1.2 GPa using X‐ray absorption spectroscopy and X‐ray diffraction

The crystal and local atomic structure of monoclinic ReO₂ (α‐ReO₂) under hydrostatic pressure up to 1.2 GPa was investigated for the first time using both X‐ray absorption spectroscopy and high‐resolution synchrotron X‐ray powder diffraction and a home‐built B₄C anvil pressure cell developed for this purpose. Extended X‐ray absorption fine‐structure (EXAFS) data analysis at pressures from ambient up to 1.2 GPa indicates that there are two distinct Re—Re distances and a distorted ReO₆ octahedron in the α‐ReO₂ structure. X‐ray diffraction analysis at ambient pressure revealed an unambiguous solution for the crystal structure of the α‐phase, demonstrating a modulation of the Re—Re distances. The relatively small portion of the diffraction pattern accessed in the pressure‐dependent measurements does not allow for a detailed study of the crystal structure of α‐ReO₂ under pressure. Nonetheless, a shift and reduction in the (011) Bragg peak intensity between 0.4 and 1.2 GPa is observed, with correlation to a decrease in Re—Re distance modulation, as confirmed by EXAFS analysis in the same pressure range. This behavior reveals that α‐ReO₂ is a possible inner pressure gauge for future experiments up to 1.2 GPa.     

Propagation of an X‐ray beam modified by a photonic crystal

A method of calculating the transmission of hard X‐ray radiation through a perfect and well oriented photonic crystal and the propagation of the X‐ray beam modified by a photonic crystal in free space is developed. The method is based on the approximate solution of the paraxial equation at short distances, from which the recurrent formula for X‐ray propagation at longer distances is derived. A computer program for numerical simulation of images of photonic crystals at distances just beyond the crystal up to several millimetres was created. Calculations were performed for Ni inverted photonic crystals with the [111] axis of the face‐centred‐cubic structure for distances up to 0.4 mm with a step size of 4 µm. Since the transverse periods of the X‐ray wave modulation are of several hundred nanometres, the intensity distribution of such a wave is changed significantly over the distance of several micrometres. This effect is investigated for the first time.     

Quantitative performance measurements of bent crystal Laue analyzers for X‐ray fluorescence spectroscopy

Third‐generation synchrotron radiation sources pose difficult challenges for energy‐dispersive detectors for XAFS because of their count rate limitations. One solution to this problem is the bent crystal Laue analyzer (BCLA), which removes most of the undesired scatter and fluorescence before it reaches the detector, effectively eliminating detector saturation due to background. In this paper experimental measurements of BCLA performance in conjunction with a 13‐element germanium detector, and a quantitative analysis of the signal‐to‐noise improvement of BCLAs are presented. The performance of BCLAs are compared with filters and slits.     

Silicon nitride transmission X‐ray mirrors

Transmission X‐ray mirrors have been fabricated from 300–400 nm‐thick low‐stress silicon nitride windows of size 0.6 mm × 85 mm. The windows act as a high‐pass energy filter at grazing incidence in an X‐ray beam for the beam transmitted through the window. The energy cut‐off can be selected by adjusting the incidence angle of the transmission mirror, because the energy cut‐off is a function of the angle of the window with respect to the beam. With the transmission mirror at the target angle of 0.22°, a 0.3 mm × 0.3 mm X‐ray beam was allowed to pass through the mirror with a cut‐off energy of 10 keV at the Cornell High Energy Synchrotron Source. The energy cut‐off can be adjusted from 8 to 12 keV at an angle of 0.26° to 0.18°, respectively. The observed mirror transmittance was above 80% for a 300 nm‐thick film.