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1. Syntheses and crystal structures of three triphenylsulfonium salts of manganese(II), iron(III) and cobalt(II)

   https://doi.org/10.1107/S2056989025006668  

   Callaway, Waylan; Elterman, Matthew; Krasilnikov, Nikita; Roberts, Gavin; Rutan, Davis; Spencer, Ty; Padgett, Clifford W; Lynch, Will E (August 2025, Acta Crystallographica Section E Crystallographic Communications)

   Bis(triphenylsulfonium) tetrachloridomanganate(II), (C₁₈H₁₅S)₂[MnCl₄] (I), triphenylsulfonium tetrachloridoferrate(III), (C₁₈H₁₅S)[FeCl₄] (II), and bis(triphenylsulfonium) tetrachloridocobaltate(II), (C₁₈H₁₅S)₂[CoCl₄] (III), crystallize in the monoclinic space groupsP2₁/n[(I) and (III)] andP2₁/c[(II)]. Compounds (I) and (III) each contain two crystallographically independent triphenylsulfonium (TPS⁺) cations in the asymmetric unit, whereas (II) has one. In all three compounds, the sulfonium centers adopt distorted trigonal–pyramidal geometries, with S—C bond lengths falling roughly in the 1.78–1.79 Å range and C—S—C angles observed at about 101 to 106°. The [MCl₄]ⁿ⁻anions (M= Mn²⁺, Fe³⁺, Co²⁺;n= 2,1,2) adopt slightly distorted tetrahedral geometries, withM—Cl bond lengths in the 2.19–2.38 Å range and Cl—M—Cl angles of approximately 104–113°. Hirshfeld surface analyses shows that H...H and H...C contacts dominate the TPS⁺cation environments, whereas H...Cl and shortM—S interactions link each [MCl₄]ⁿ⁻anion to the surrounding cations. In (I) and (III), inversion-centered π–π stacking further consolidates the crystal packing, while in (II) no π–π interactions are observed. 

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2. Investigating the [C ii]-to-H i Conversion Factor and the H i Gas Budget of Galaxies at z ≈ 6 with Hydrodynamic Simulations

   https://doi.org/10.3847/2041-8213/ac982c  

   Vizgan, David; Heintz, Kasper E.; Greve, Thomas R.; Narayanan, Desika; Davé, Romeel; Olsen, Karen P.; Popping, Gergö; Watson, Darach (October 2022, The Astrophysical Journal Letters)

   Abstract One of the most fundamental baryonic matter components of galaxies is the neutral atomic hydrogen (Hi). At low redshifts, this component can be traced directly through the 21 cm transition, but to infer the Higas content of the most distant galaxies, a viable tracer is needed. We here investigate the fidelity of the fine-structure transition of the (²P_3/2−²P_1/3) transition of singly ionized carbon Ciiat 158μm as a proxy for Hiin a set simulated galaxies atz≈ 6, following the work by Heintz et al. We select 11,125 star-forming galaxies from thesimbasimulations, with far-infrared line emissions postprocessed and modeled within the Sigameframework. We find a strong connection between Ciiand Hi, with the relation between this Cii-to-Hirelation (β_[CII]) being anticorrelated with the gas-phase metallicity of the simulated galaxies. We further use these simulations to make predictions for the total baryonic matter content of galaxies atz≈ 6, and specifically the Higas mass fraction. We find mean values ofM_{H I}/M_⋆= 1.4 andM_{H I}/M_bar,tot= 0.45. These results provide strong evidence for Hibeing the dominant baryonic matter component by mass in galaxies atz≈ 6. 

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3. Monovalent lanthanide(I) in borozene complexes

   https://doi.org/10.1038/s41467-021-26785-9  

   Li, Wan-Lu; Chen, Teng-Teng; Chen, Wei-Jia; Li, Jun; Wang, Lai-Sheng (November 2021, Nature Communications)

   Abstract Lanthanide (Ln) elements are generally found in the oxidation state +II or +III, and a few examples of +IV and +V compounds have also been reported. In contrast, monovalent Ln(+I) complexes remain scarce. Here we combine photoelectron spectroscopy and theoretical calculations to study Ln-doped octa-boron clusters (LnB₈⁻, Ln = La, Pr, Tb, Tm, Yb) with the rare +I oxidation state. The global minimum of the LnB₈⁻species changes fromC_stoC_7vsymmetry accompanied by an oxidation-state change from +III to +I from the early to late lanthanides. All theC_7v-LnB₈⁻clusters can be viewed as a monovalent Ln(I) coordinated by a η⁸-B₈²⁻doubly aromatic ligand. The B₇³⁻, B₈²⁻, and B₉⁻series of aromatic boron clusters are analogous to the classical aromatic hydrocarbon molecules, C₅H₅⁻, C₆H₆, and C₇H₇⁺, respectively, with similar trends of size and charge state and they are named collectively as “borozenes”. Lanthanides with variable oxidation states and magnetic properties may be formed with different borozenes. 

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4. Crystal structures of three salts of the triphenylsulfonium ion

   https://doi.org/10.1107/S2056989025000118  

   Artis, Rylan; Callaway, Waylan; Heyward, Elizabeth; Reyes, Naomi; Roberts, Gavin; Van_Ostenbridge, Kaitlyn; Padgett, Clifford W; Lynch, Will E (February 2025, Acta Crystallographica Section E Crystallographic Communications)

   The reactions of triphenylsulfonium chloride ([TPS][Cl]) with various acids in methanol yield the corresponding salts triphenylsulfonium triiodide, C₁₈H₁₅S⁺·I₃⁻or [TPS][I₃] (I), triphenylsulfonium perchlorate, C₁₈H₁₅S⁺·ClO₄⁻or [TPS][ClO₄] (II), and triphenylsulfonium hexafluorophosphate, C₁₈H₁₅S⁺·PF₆⁻or [TPS][PF₆] (III), as crystalline products. These crystals were structurally characterized by single-crystal X-ray diffraction. In all three compounds, the sulfur atom in the triphenylsulfonium cation adopts a distorted trigonal–pyramidal geometry. [TPS][I₃] (I) and [TPS][PF₆](III) both crystallize in the space groupP2₁/n, while [TPS][ClO₄] (II) crystallizes inP2₁. The S—C bond lengths are comparable across the three salts, and the S—C—S bond angles are consistently between 102 and 106°. Hirshfeld surface analyses reveal that each structure is dominated by hydrogen-based intermolecular contacts, supplemented by anion-specific interactions such as I...H in (I), O...H in (II), and F...H in (III). These contacts organize the ions into mono-periodic ribbon- or chain-like arrangements. No significant π–π stacking is observed. 

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5. Photodriven Elimination of Chlorine From Germanium and Platinum in a Dinuclear Pt ^II →Ge ^IV Complex

   https://doi.org/10.1002/anie.202107485  

   Karimi, Mohammadjavad; Tabei, Elham S.; Fayad, Remi; Saber, Mohamed R.; Danilov, Evgeny O.; Jones, Cameron; Castellano, Felix N.; Gabbaï, François P. (September 2021, Angewandte Chemie International Edition)

   Abstract Searching for a connection between the two‐electron redox behavior of Group‐14 elements and their possible use as platforms for the photoreductive elimination of chlorine, we have studied the photochemistry of [(o‐(Ph₂P)C₆H₄)₂Ge^IVCl₂]Pt^IICl₂and [(o‐(Ph₂P)C₆H₄)₂ClGe^III]Pt^IIICl₃, two newly isolated isomeric complexes. These studies show that, in the presence of a chlorine trap, both isomers convert cleanly into the platinum germyl complex [(o‐(Ph₂P)C₆H₄)₂ClGe^III]Pt^ICl with quantum yields of 1.7 % and 3.2 % for the Ge^IV–Pt^IIand Ge^III–Pt^IIIisomers, respectively. Conversion of the Ge^IV–Pt^IIisomer into the platinum germyl complex is a rare example of a light‐induced transition‐metal/main‐group‐element bond‐forming process. Finally, transient‐absorption‐spectroscopy studies carried out on the Ge^III–Pt^IIIisomer point to a ligand arene–Cl^.charge‐transfer complex as an intermediate. 

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