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Title: TOI-677b: A Warm Jupiter ( P = 11.2 days) on an Eccentric Orbit Transiting a Late F-type Star
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  1. This work raises a fundamental question about the “real” structure of molecular compounds containing three different metals: whether they consist of genuine hetero tri metallic species or of a mixture of parent hetero bi metallic species. Heterotrimetallic complex Li 2 CoNi(tbaoac) 6 ( 1 , tbaoac = tert -butyl acetoacetate) has been designed based on the model tetranuclear structure featuring two transition metal sites in order to be utilized as a molecular precursor for the low-temperature preparation of the LiCo 0.5 Ni 0.5 O 2 battery cathode material. An investigation of the structure of 1 appeared to be very challenging, since the Co and Ni atoms have very similar atomic numbers, monoisotopic masses, and radii as well as the same oxidation state and coordination number/environment. Using a statistical analysis of heavily overlaid isotope distribution patterns of the [Li 2 MM′L 5 ] + (M/M′ = Co 2 , Ni 2 , and CoNi) ions in DART mass spectra, it was concluded that the reaction product 1 contains both heterotrimetallic and bimetallic species. A structural analogue approach has been applied to obtain Li 2 MMg(tbaoac) 6 (M = Co ( 2 ) and Ni ( 3 )) complexes that contain lighter, diamagnetic magnesium in the place of one of the 3d transition metals. X-ray crystallography, mass spectrometry, and NMR spectroscopy unambiguously confirmed the presence of three types of molecules in the reaction mixture that reaches an equilibrium, Li 2 M 2 L 6 + Li 2 Mg 2 L 6 ↔ 2Li 2 MMgL 6 , upon prolonged reflux in solution. The equilibrium mixture was shown to have a nearly statistical distribution of the three molecules, and this is fully supported by the results of theoretical calculations revealing that the stabilization energies of hetero tri metallic assemblies fall exactly in between those for the parent hetero bi metallic species. The LiCo 0.5 Ni 0.5 O 2 quaternary oxide has been obtained in its phase-pure form by thermal decomposition of heterometallic precursor 1 at temperatures as low as 450 °C. Its chemical composition, structure, morphology, and transition metal distribution have been studied by X-ray and electron diffraction techniques and compositional energy-dispersive X-ray mapping with nanometer resolution. The work clearly illustrates the advantages of heterometallic single-source precursors over the corresponding multi-source precursors. 
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  2. null (Ed.)
    ABSTRACT X-ray observations provide a unique probe of the accretion disc corona of supermassive black holes (SMBHs). In this paper, we present a uniform Chandra X-ray data analysis of a sample of 152 z ≥ 4.5 quasars. We firmly detect 46 quasars of this sample in 0.5–2 keV above 3σ and calculate the upper limits of the X-ray flux of the remaining. We also estimate the power-law photon index of the X-ray spectrum of 31 quasars. 24 of our sample quasars are detected in the FIRST or NVSS radio surveys; all of them are radio-loud. We statistically compare the X-ray properties of our z ≥ 4.5 quasars to other X-ray samples of active galactic nuclei (AGNs) at different redshifts. The relation between the rest-frame X-ray luminosity and other quasar parameters, such as the bolometric luminosity, UV luminosity, or SMBH mass, shows large scatters. These large scatters can be attributed to the narrow luminosity range at the highest redshift, the large measurement error based on relatively poor X-ray data, and the inclusion of radio-loud quasars in the sample. The LX–LUV relationship is significantly sublinear. We do not find a significant redshift evolution of the LX–LUV relation, expressed either in the slope of this relation, or the departure of individual AGNs from the best-fitting αOX–LUV relation (ΔαOX). The median value of the X-ray photon index is Γ ≈ 1.79, which does not show redshift evolution from z = 0 to z ∼ 7. The X-ray and UV properties of the most distant quasars could potentially be used as a standard candle to constrain cosmological models. The large scatter of our sample on the Hubble diagram highlights the importance of future large unbiased deep X-ray and radio surveys in using quasars in cosmological studies. 
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