Au Distance Research Articles

Structural, Electrochemical, and Photochemical Properties of Mono‐ and Digold(I) Complexes Containing Mesoionic Carbenes

Triazolylidenes are a prominent class of mesoionic carbenes (MICs) that are currently widely used in organometallic chemistry. Usually the metal complexes of such ligands are used as homogeneous catalysts even though they have vast potential in other branches of chemistry. We present here three related gold(I) complexes with MIC ligands: a neutral mononuclear chlorido complex [AuCl(MIC)], a cationic mononuclear complex containing two MIC ligands [Au(MIC)2]BF4, and a dicationic digold(I) complex containing two di‐MIC ligands [Au2(κ1,κ1,µ‐di‐MIC)2](BF4)2. The complexes were characterized by 1H and 13C{1H} NMR spectroscopy, mass spectrometry, and single‐crystal X‐ray diffraction. The gold(I) centers are linearly coordinated through either one MIC‐C and chlorido donors or through two MIC‐C donors. The triazolylidenes display a delocalized bonding situation within the ring. Additionally, a short Au–Au distance of about 3 Å is observed for the digold(I) complex. All complexes display reduction steps in their cyclic voltammograms, and these are assigned to the reduction of the MIC ligands, as opposed to the generation of gold(0). The complexes emit at ca. 500 nm, with lifetimes of several microseconds in deoxygenated solutions; the emission intensity and lifetime are strongly decreased by the presence of oxygen, supporting the triplet origin of the emissive state. The present results display the utility of MIC ligands for generating electro‐ and photoactive molecules.

Preparation of gold-containing binary metal clusters by co-deposition-precipitation method and for hydrogenation of chloronitrobenzene

Nano-gold catalyst has been reported to have high activity and selectivity for liquid phase hydrogenation reaction. In this study, gold-containing bimetals were loaded on TiO2. For bimetallic catalysts, gold and different metals were prepared by the deposition-precipitation method, and then used NaBH4 to reduce metal cations. The catalysts were characterized by X-ray diffraction, transmission electron microscopy, high resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. The catalytic properties of these catalysts were tested by hydrogenation of p-chloronitrobenzene (p-CNB) in a batch reactor at 1.1 MPa H2 pressure, 373 K and 500 rpm. Cu, Ag, Ru, and Pd formed nano-alloy with Au. In addition, Cu–Au, Ag–Au, and Ru–Au alloy had Cu-, Ag-, and Ru-enriched surface, respectively. Instead, Pd–Au alloy had Pd-enriched surface. There are two kinds of alloy effects: (1) geometric effects, i.e., the surface-enriched metal would change the distance of Au–Au atoms that is required for facilitating the hydrogenation of chloronitrobenzene; and (2) electronic effects, which involve charge transfer between the metals. The activity decreased in the following order: PdAu/TiO2 > Au/TiO2 > NiAu/TiO2 > AgAu/TiO2 > RuAu/TiO2 > CuAu/TiO2. Comparing with other metals, adding Pd in Au showed a higher activity. Adding palladium could reduce gold-valence state, and increased active sites for reaction.

Atmospheric trajectory and heliocentric orbit of the Ejby meteorite fall in Denmark on February 6, 2016

A very bright bolide illuminated the sky over Denmark and neighboring countries on February 6th, 2016 at 21:07:18-23UT. It terminated by a multiple meteorite fall in the heavily populated area of the western outskirts of Copenhagen. Several meteorites classified as the H5/6 ordinary chondrites have been found shortly after the fall and total recovered mass reached almost 9kg (Haack, 2016). Although this spectacular bolide has been reported by many casual witnesses, the instrumental records are very scarce, mainly due to bad weather over Denmark and neighboring countries. Despite it we were able to collect five instrumental records taken from different locations which were useful for the analysis of this event. We used three high resolution digital photographic images taken in Germany, one high resolution radiometric light curve taken by the northernmost Czech automated fireball observatory and one video record taken by a surveillance camera on the Danish west coast where a part of the fireball trajectory was recorded. It allowed us to reliably determine basic parameters defining the luminous trajectory of the bolide in the atmosphere and also heliocentric orbit of the initial meteoroid causing this spectacular meteorite fall. We found that this event was caused by a relatively fragile 50cm meteoroid with initial mass about 250kg. It entered the atmosphere with velocity of 14.5kms−1 and quite steep entry angle of 62°. Its luminous flight started at 85.5km and after 76km long trajectory it terminated at 18.3km. The heliocentric orbit of this meteoroid was of Apollo type with low inclination of 1° and perihelion distance just inside the Earth's orbit. It had a relatively large semimajor axis of 2.8AU and aphelion distance 4.64AU. It is the second largest aphelion distance among all meteorites with known orbits and the orbit had the same character as that of the Košice meteorite (H5 ordinary chondrite), which fell on February 28, 2010 (Borovička et al., 2013).

DYNAMICAL CONSTRAINTS ON THE ORIGIN OF HOT AND WARM JUPITERS WITH CLOSE FRIENDS

ABSTRACT Gas giants orbiting their host star within the ice line are thought to have migrated to their current locations from farther out. Here we consider the origin and dynamical evolution of observed Jupiters, focusing on hot and warm Jupiters with outer friends. We show that the majority of the observed Jupiter pairs (20 out of 24) are dynamically unstable if the inner planet is placed at ≳1 au distance from the stellar host. This finding is at odds with formation theories that invoke the migration of such planets from semimajor axes ≳1 au due to secular dynamical processes (e.g., secular chaos, Lidov–Kozai [LK] oscillations) coupled with tidal dissipation. In fact, the results of N-body integrations show that the evolution of dynamically unstable systems does not lead to tidal migration but rather to planet ejections and collisions with the host star. This and other arguments lead us to suggest that most of the observed planets with a companion could not have been transported from farther out through secular migration processes. More generally, by using a combination of numerical and analytic techniques, we show that the high-e LK migration scenario can only account for less than 10% of all gas giants observed between 0.1 and 1 au. Simulations of multiplanet systems support this result. Our study indicates that rather than starting on highly eccentric orbits with orbital periods above 1 yr, these “warm” Jupiters are more likely to have reached the region where they are observed today without having experienced significant tidal dissipation.

Mono- and Digold(I) Complexes with Mesoionic Carbenes: Structural Characterization and Use in Catalytic Silver-Free Oxazoline Formation

Triazolylidenes are a prominent class of mesoionic carbenes that have found use as supporting ligands in homogeneous catalysis in recent years. We present here the syntheses of three new mononuclear gold(I) chlorido and two new dinuclear gold(I) chlorido complexes. The ligands in the aforementioned complexes are derived from either the corresponding monotriazolium or the bitriazolium salts. All complexes have been characterized by 1H and 13C{1H} NMR spectroscopy, mass spectrometry, and single-crystal X-ray diffraction studies. Structural characterization delivers a delocalized bonding situation within the triazolylidene ligands and a linear coordination at the gold(I) centers. The gold(I) centers in all cases are bound to one triazolylidene-C donor and a chlorido ligand. Additionally, for the digold(I) complexes large Au–Au distances were observed, ruling out the existence of aurophilic interactions in these digold complexes in the solid state. All of the gold(I) complexes were tested as (pre)catalysts fo...

ROCKY PLANET FORMATION: QUICK AND NEAT

ABSTRACT We reconsider the commonly held assumption that warm debris disks are tracers of terrestrial planet formation. The high occurrence rate inferred for Earth-mass planets around mature solar-type stars based on exoplanet surveys (∼20%) stands in stark contrast to the low incidence rate (≤2%–3%) of warm dusty debris around solar-type stars during the expected epoch of terrestrial planet assembly (∼10 Myr). If Earth-mass planets at au distances are a common outcome of the planet formation process, this discrepancy suggests that rocky planet formation occurs more quickly and/or is much neater than traditionally believed, leaving behind little in the way of a dust signature. Alternatively, the incidence rate of terrestrial planets has been overestimated, or some previously unrecognized physical mechanism removes warm dust efficiently from the terrestrial planet region. A promising removal mechanism is gas drag in a residual gaseous disk with a surface density ≳10−5 of the minimum-mass solar nebula.

DETAILED ANALYSIS OF NEAR-IR WATER (H2O) EMISSION IN COMET C/2014 Q2 (LOVEJOY) WITH THE GIANO/TNG SPECTROGRAPH

ABSTRACT We observed the Oort cloud comet C/2014 Q2 (Lovejoy) on 2015 January 31 and February 1 and 2 at a heliocentric distance of 1.3 au and geocentric distance of 0.8 au during its approach to the Sun. Comet Lovejoy was observed with GIANO, the near-infrared high-resolution spectrograph mounted at the Nasmyth-A focus of the TNG (Telescopio Nazionale Galileo) telescope in La Palma, Canary Islands, Spain. We detected strong emissions of radical CN and water, along with many emission features of unidentified origin, across the 1–2.5 μm region. Spectral lines from eight ro-vibrational bands of H2O were detected, six of them for the first time. We quantified the water production rate [Q(H2O), (3.11 ± 0.14) × 1029 s−1] by comparing the calibrated line fluxes with the Goddard full non-resonance cascade fluorescence model for H2O. The production rates of ortho-water [Q(H2O)ORTHO, (2.33 ± 0.11) × 1029 s−1] and para-water [Q(H2O)PARA, (0.87 ± 0.21) × 1029 s−1] provide a measure of the ortho-to-para ratio (2.70 ± 0.76)). The confidence limits are not small enough to provide a critical test of the nuclear spin temperature.

Bonding, Luminescence, Metallophilicity in Linear Au3 and Au2Ag Chains Stabilized by Rigid Diphosphanyl NHC Ligands.

The heterofunctional and rigid ligand N,N'-diphosphanyl-imidazol-2-ylidene (PCNHCP; P = P(t-Bu)2), through its phosphorus and two N-heterocyclic carbene (NHC) donors, stabilizes trinuclear chain complexes, with either Au3 or AgAu2 cores, and dinuclear Au2 complexes. The two oppositely situated PCNHCP (L) ligands that "sandwich" the metal chain can support linear and rigid structures, as found in the known tricationic Au(I) complex [Au3(μ3-PCNHCP,κP,κCNHC,κP)2](OTf)3 (OTf = CF3SO3; [Au3L2](OTf)3; Chem. Commun. 2014, 50, 103-105) now also obtained by transmetalation from [Ag3(μ3-PCNHCP,κP,κCNHC,κP)2](OTf)3 ([Ag3L2](OTf)3), or in the mixed-metal tricationic [Au2Ag(μ3-PCNHCP,κP,κCNHC,κP)2](OTf)3 ([Au2AgL2](OTf)3). The latter was obtained stepwise by the addition of AgOTf to the digold(I) complex [Au2(μ2-PCNHCP,κP,κCNHC)2](OTf)2 ([Au2L2](OTf)2). The latter contains two dangling P donors and displays fluxional behavior in solution, and the Au···Au separation of 2.8320(6) Å in the solid state is consistent with metallophilic interactions. In the solvento complex [Au3Cl2(tht)(μ3-PCNHCP,κP,κCNHC,κP)](OTf)·MeCN ([Au3Cl2(tht)L](OTf)·MeCN), which contains only one L and one tht ligand (tht = tetrahydrothiophene), the metal chain is bent (148.94(2)°), and the longer Au···Au separation (2.9710(4) Å) is in line with relaxation of the rigidity due to a more "open" structure. Similar features were observed in [Au3Cl2(SMe2)L](OTf)·2MeCN. A detailed study of the emission properties of [Au3L2](OTf)3, [Au3Cl2(tht)L](OTf)·MeCN, [Au2L2](OTf)2, and [Au2AgL2](OTf)3 was performed by means of steady state and time-resolved photophysical techniques. The complex [Au3L2](OTf)3 displays a bright (photoluminescence quantum yield = 80%) and narrow emission band centered at 446 nm with a relatively small Stokes' shift and long-lived excited-state lifetime on the microsecond timescale, both in solution and in the solid state. In line with the very narrow emission profile centered in the violet-blue region, fabrication of organic light-emitting devices (OLEDs) comprising the [Au3L2](OTf)3 complex demonstrated its usefulness as a deep-blue emitter in solution-processed OLEDs. Electrochemical and Raman spectroscopic studies were also performed on [Au3L2](OTf)3. Experimental results were rationalized by means of Wave-Function Theory (WFT) and Density Functional Theory (DFT). MP2 calculations gave a satisfactory description of the structures of the cationic complexes [Au3L2](3+) and [Au2L2](2+) and pointed to Au···Au interactions having an electrostatic component owing to the dissimilar charge distribution in the chain caused by the heterofunctional ligand. The nature of the emitting states and their geometric distortions relative to the ground states in [Au3L2](3+) and [Au2L2](2+) was studied by DFT, revealing contraction of the Au···Au distances and coordination geometry changes by association of the dangling P donor, respectively.

MICROLENSING PARALLAX FOR OBSERVERS IN HELIOCENTRIC MOTION

ABSTRACT Motivated by the ongoing Spitzer observational campaign, and the forthcoming K2 one, we revisit, working in an heliocentric reference frame, the geometrical foundation for the analysis of the microlensing parallax, as measured with the simultaneous observation of the same microlensing event from two observers with relative distance of order au. For the case of observers at rest, we discuss the well-known fourfold microlensing parallax degeneracy and determine an equation for the degenerate directions of the lens trajectory. For the case of observers in motion, we write down an extension of the Gould relationship between the microlensing parallax and the observable quantities and, at the same time, highlight the functional dependence of these same quantities from the timescale of the underlying microlensing event. Furthermore, through a series of examples, we show the importance of taking into account themotion of the observers to correctly recover the parameters of the underlying microlensing event. In particular, we discuss the cases of the amplitude of the microlensing parallax and that of the difference of the timescales between the observed microlensing events, which are key to understand the breaking of the microlensing parallax degeneracy. Finally, we consider the case of the simultaneous observation of the same microlensing event from the ground and two satellites, a case relevant for the expected joint K2 and Spitzer observational programs in 2016.

DISTANCE TO THE IBEX RIBBON SOURCE INFERRED FROM PARALLAX

ABSTRACT Maps of energetic neutral atom (ENA) fluxes obtained from observations made by the Interstellar Boundary Explorer (IBEX) revealed a bright structure extending over the sky, subsequently dubbed the IBEX ribbon. The ribbon had not been expected from the existing models and theories prior to IBEX, and a number of mechanisms have since been proposed to explain the observations. In these mechanisms, the observed ENAs emerge from source plasmas located at different distances from the Sun. Since each part of the sky is observed by IBEX twice during the year from opposite sides of the Sun, the apparent position of the ribbon as observed in the sky is shifted due to parallax. To determine the ribbon’s parallax, we found the precise location of the maximum signal of the ribbon observed in each orbital arc. The apparent positions obtained were subsequently corrected for the Compton–Getting effect, gravitational deflection, and radiation pressure. Finally, we selected a part of the ribbon where its position is similar in the different IBEX energy passbands. We compared the apparent positions obtained from the viewing locations on the opposite sides of the Sun, and found that they are shifted by a parallax angle of 0.°41 ± 0.°15, which corresponds to a distance of AU. This finding supports models of the ribbon with the source located just outside the heliopause.

RADIO EMISSION FROM RED-GIANT HOT JUPITERS

ABSTRACT When planet-hosting stars evolve off the main sequence and go through the red-giant branch, the stars become orders of magnitudes more luminous and, at the same time, lose mass at much higher rates than their main-sequence counterparts. Accordingly, if planetary companions exist around these stars at orbital distances of a few au, they will be heated up to the level of canonical hot Jupiters and also be subjected to a dense stellar wind. Given that magnetized planets interacting with stellar winds emit radio waves, such “Red-Giant Hot Jupiters” (RGHJs) may also be candidate radio emitters. We estimate the spectral auroral radio intensity of RGHJs based on the empirical relation with the stellar wind as well as a proposed scaling for planetary magnetic fields. RGHJs might be intrinsically as bright as or brighter than canonical hot Jupiters and about 100 times brighter than equivalent objects around main-sequence stars. We examine the capabilities of low-frequency radio observatories to detect this emission and find that the signal from an RGHJ may be detectable at distances up to a few hundred parsecs with the Square Kilometer Array.

Dinuclear Au(i) N-heterocyclic carbene complexes derived from unsymmetrical azolium cyclophane salts: potential probes for live cell imaging applications.

We have synthesized a new series of azolium cyclophanes and used them as precursors of inherently luminescent dinuclear Au(i)-N-heterocyclic carbene (NHC) complexes. The azolium cyclophanes contained two azolium groups (either imidazolium or benzimidazolium), an o-xylyl group, and an alkyl linker chain (either C2, C3 or C4). All of the azolium cyclophanes were characterised by X-ray diffraction studies and VT NMR studies, and all were fluxional in solution on the NMR timescale. The C3- and C4-linked azolium cyclophanes served as precursors of Au2L2(2+) complexes (L is a cyclophane bis(NHC) ligand). Due to the unsymmetrical nature of the azolium cyclophanes, the Au2L2(2+) complexes each existed as cis and trans isomers. X-ray diffraction studies showed that the Au2L2(2+) complexes had short intramolecular AuAu distances, in the range 2.9-3.3 Å, suggestive of an aurophilic attraction, presumably as a consequence of the geometrical constraints imposed by the cyclophane bis(NHC) ligands. The complexes having the shortest AuAu distances (i.e., those based on C3-linked cyclophanes) exhibited intense luminescence in solution. The uptake of one of the dinuclear Au-NHC complexes by tumorigenic cells, and its subsequent distribution and toxicity in the cells, was monitored by luminescence microscopy over 6 h and proliferation measurements, respectively.

Mineral prospectivity mapping with weights of evidence and fuzzy logic methods

Knowledge-and data-driven approaches are two major methods used to integrate various evidential maps for mineral prospectivity mapping (MPM). Geological maps, geochemical samples and data from known gold deposits were collected in the western Junggar area, Xinjiang Province. The geological and a spatial database for geological and mineral occurrences were constructed for the studied region. A weights-of-evidence model and a fuzzy logic model were employed for MPM, and the results were compared. Results indicate that favorable sedimentary rocks, fault density, fault distance and concentration of Au were the primary factors affecting Au mineralization. Arsenic (AS), Stibium (Sb), fault direction, quartz veins and intrusive rocks were secondary factors affecting Au mineralization. Conditional independence exerted a major influence on the weights-of-evidence model. However, posterior probability would be very high if the conditional independence was disregarded, which impaired results. Combining the quantification results provided by weights-of-evidence and the fuzzy membership values determined by expert knowledge, the mineral prospectivity mapping according to the fuzzy logic method was proved to be valid. For the study area, which had a large number of deposits, data-driven approaches for MPM are generally considered to be appropriate. However, if sufficient data are not collected, the knowledge-driven approaches, for example, the fuzzy logic method used in the present study, usually achieves a better result.

Methyl‐, Ethenyl‐, and Ethynyl‐Bridged Cationic Digold Complexes Stabilized by Coordination to a Bulky Terphenylphosphine Ligand

AbstractReactions of the gold(I) triflimide complex [Au(NTf2)(PMe2Ar${{^{{\rm Dipp}{_{2}}}}}$)] (1) with the gold(I) hydrocarbyl species [AuR(PMe2Ar${{^{{\rm Dipp}{_{2}}}}}$)] (2 a–2 c) enable the isolation of hydrocarbyl‐bridged cationic digold complexes with the general composition [Au2(μ‐R)(PMe2Ar${{^{{\rm Dipp}{_{2}}}}}$)2][NTf2], where Ar${{^{{\rm Dipp}{_{2}}}}}$=C6H3‐2,6‐(C6H3‐2,6‐iPr2)2 and R=Me (3), CHCH2 (4), or CCH (5). Compound 3 is the first alkyl‐bridged digold complex to be reported and features a symmetric [Au(μ‐CH3)Au]+ core. Complexes 4 and 5 are the first species of their kind that contain simple, unsubstituted vinyl and acetylide units, respectively. In the series of complexes 3–5, the bridging carbon atom systematically changes its hybridization from sp3 to sp2 and sp. Concomitant with this change, and owing to variations in the nature of the bonding within the [Au(μ‐R)Au]+ unit, there is a gradual decrease in aurophilicity, that is, the strength of the Au⋅⋅⋅Au bonding interaction decreases. This change is illustrated by a monotonic increase in the Au–Au distance by approximately 0.3 Å from R=CH3 (2.71 Å) to CHCH2 (3.07 Å) and CCH (3.31 Å).

Synthesis and thermotropic behaviour of bis(imidazolium) salts bearing long-chain alkyl-substituents and of the corresponding dinuclear gold carbene complexes

New propylene bridged bis(imidazolium) salts bearing at the wingtip positions a benzyl group functionalised with one or two long alkyl chains, as well as the corresponding dinuclear N-heterocyclic dicarbene gold(I) complexes of general formula [Au2(RIm–(CH2)3–ImR)2](X)2 (X = Br, PF6, BF4) have been synthesised and thermally characterised. All the compounds are stable up to 200 °C and the bis(imidazolium) salts [H2(RIm–(CH2)3–ImR)](X)2 (X = Br, PF6) behave as thermotropic liquid crystals in the temperature range 100–200 °C. By contrast, only the gold(I) diNHC complexes with eight aliphatic chains present mesomorphism, whereas those with four chains show numerous crystalline phases with structural disorder and presumably modified Au–Au distances, as indicated by solid state emission properties.

Chemisorption binding of gold(III) from solutions with bismuth dipropyldithiocarbamate: Supramolecular self-assembly (role of the secondary Au…S and aurophilic interactions) and thermal behavior of the solvated heteropolynuclear ionic type complex ([Au{S2CN(C3H7)2}2]3[Bi2Cl9] • 0.5CO(CH3)2 • 0.5HCl) n

The reaction of binuclear bismuth(III) N,N-dipropyldithiocarbamate [Bi2{S2CN(C3H7)2}6] with a solution of AuCl3 in 2 M HCl was studied. Crystallization of the heterogeneous reaction products from an acetone solution afforded the polymeric solvated heteropolynuclear gold(III)–bismuth complex, ([Au{S2CN(C3H7)2}2]3[Bi2Cl9] · 1/2CO(CH3)2 · 1/2HCl)n (I). According to X-ray diffraction data (CIF file CCDC no. 1050766), the structure of I comprises four isomeric [Au{S2CN(C3H7)2}2]+ cations in 1: 1: 2: 2 ratio, namely: cation “A” with the Au(1) atom, cation “B” with the Au(2) atom, cation “C” with the Au(3) atom, and cation “D” with the Au(4) atom, and the discrete binuclear [Bi2Cl9]3– anions. The isomeric gold(III) complex cations are involved in the construction of two types of cationic triads, [“C”···“A”···“C”] and [“D”···“B”···“D”], through secondary bonds and short Au···S contacts. The cation types differ by both the nature of binding and the Au–Au distances. The weak aurophilic binding between the cationic triads (Au···Au 3.5416(2) A) gives rise to zigzag-like polymeric chains (···[“C”···“A”···“C”]···[“D”···“B”···“D”]···)n extended along the y axis. In turn, the [Bi2Cl9]3– anions located on one side of polymer chains are held by the secondary Cl···S bonds. The outer-sphere CO(CH3)2 and HCl solvate molecules joined by hydrogen bonds are located in the space between bismuth anions. The thermal behavior of I was studied by simultaneous thermal analysis. The thermal destruction of the complex includes desolvation and thermolysis of the dithiocarbamate moiety and [Bi2Cl9]3– with liberation of gold metal and bismuth chloride (which is subsequently evaporated) and partial formation of Bi2S3. In the temperature range of 712–828°C, bismuth sulfide is oxidized to (BiO)2SO4, which decomposes above 828°C to give Bi2O3. Bismuth(III) oxide and reduced gold are the final products of thermal transformations.

Ca4Au10Zn3 – A Substitution Variant of AlB2 by Incorporation of Zn3 Triangles

AbstractThe gold‐rich intermetallic phase Ca4Au10Zn3 was synthesized from the elements by high‐frequency melting in sealed tantalum ampoules. Analyses of the sample by X‐ray powder and single crystal diffraction indicated a new structure type with a small homogeneity range resulting from Au/Zn mixing: C2/c, a = 1598.4(2), b = 819.7(1), c = 1188.2(2) pm, β = 120.93(1)°, wR2 = 0.0397, 2292 F2 values, 83 variables for Ca4Au9.66(1)Zn3.34(1), and a = 1596.6(2), b = 818.8(2), c = 1187.1(2) pm, β = 120.91(2)°, wR2 = 0.0280, 2296 F2 values, 83 variables for Ca4Au9.98(1)Zn3.02(1). The gold atoms built up a three‐dimensional distorted tetrahedral network with Au–Au distances ranging from 274–294 pm. The cavities within this network are filled by calcium atoms and Zn3 triangles (272–279 pm Zn–Zn) in an ordered manner. The small homogeneity range Ca4Au10–xZn3+x concerns Au/Zn mixing within the triangles and the tetrahedral network as well. The crystal chemical relationship with the aristotype AlB2 is discussed on the basis of a group‐subgroup scheme.

The young low-mass star ISO-Oph-50: extreme variability induced by a clumpy, evolving circumstellar disc

ISO-Oph-50 is a young low-mass object in the ~Myr old Ophiuchus star forming region undergoing dramatic changes in its optical/near/mid-infrared brightness by 2-4 mag. We present new multi-band photometry and near-infrared spectra, combined with a synopsis of the existing literature data. Based on the spectroscopy, the source is confirmed as a mid M dwarf, with evidence for ongoing accretion. The near-infrared lightcurves show large-scale variations, with 2-4 mag amplitude in the bands IJHK, with the object generally being bluer when faint. Near its brightest state, the object shows colour changes consistent with variable extinction of dAV~7 mag. High-cadence monitoring at 3.6mu reveals quasi-periodic variations with a typical timescale of 1-2 weeks. The best explanation for these characteristics is a low-mass star seen through circumstellar matter, whose complex variability is caused by changing inhomogeneities in the inner parts of the disk. When faint, the direct stellar emission is blocked; the near-infrared radiation is dominated by scattered light. When bright, the emission is consistent with a photosphere strongly reddened by circumstellar dust. Based on the available constraints, the inhomogeneities have to be located at or beyond ~0.1 AU distance from the star. If this scenario turns out to be correct, a major portion of the inner disk has to be clumpy, structured, and/or in turmoil. In its observational characteristics, this object resembles other types of YSOs with variability caused in the inner disk. Compared to other objects, however, ISO-Oph-50 is clearly an extreme case, given the large amplitude of the brightness and colour changes combined with the erratic behaviour. ISO-Oph-50 has been near its brightest state since 2013; further monitoring is highly encouraged.

Thermodynamic aspects of aurophilic hydrogelators.

The complexes [Au(4-pyridylethynyl)(phosph)] (phosph = PTA (1), DAPTA (2)) are known to produce supramolecular aggregates and gels in water. We studied the impact of these aggregation processes in the absorption spectra, (1)H NMR (at different temperatures and concentrations), and DLS and estimated the equilibrium constant for a single step aggregation of the molecule (K = 26760 and 2590 M(-1) for 1 and 2, respectively, at 25 °C). We present spectroscopic evidence for the presence of Au···Au contacts in the aggregates: the recorded changes on (1)H NMR and the appearance of new absorption bands assigned to (σ*Au···Au-π*) have been attributed to the short (Au···Au) average distances in the aggregates. Relativistic density functional theory computations support the existence of short Au···Au distances and reveal charge-transfer in the aurophilic interactions. The free energy for a single step aggregation was calculated from the experimental data, and the value obtained (ΔG ∼ -20 kJ/mol) is in good agreement with the expected values in the order of the energies found for hydrogen bonds. The DFT computations confirm the experimental findings that aggregation of monomer 1 is stronger than the aggregation of monomer 2 and the existence of aurophilic interactions.

The link between disc dispersal by photoevaporation and the semimajor axis distribution of exoplanets

We investigate the influence of photoevaporation of protoplanetary discs on the final distribution of exoplanets semimajor axis distances. We model giant planet migration in viscous discs affected by photoevaporation driven by either pure EUV or soft X-ray radiation (XEUV). We show that the final exoplanet distributions are strongly dependant on the choice of the photoevaporation model. In particular, we find that XEUV is more efficient than pure EUV radiation at parking planets at approximately 1-2 au distance from their central star, hence roughly reproducing the observed peak in the exoplanets semimajor axis distributions. We note however that a more quantitative comparison with the observations is hindered by the oversimplified treatment of planetary accretion, which severely affects migration rates. For this reason, caution should be used when using these models to constrain details of disc clearing and/or migration from the observations. Nevertheless our results indicate that disc dispersal by photoevaporation may be the main driver of the features in the exoplanets semimajor axis distribution observed by recent surveys.