skip to main content

This content will become publicly available on April 23, 2025

Title: Exploring sulfur donor atom coordination chemistry with La( ii ), Nd( ii ), and Tm( ii ) using a terphenylthiolate ligand

To expand the range of donor atoms known to stabilize 4fn5d1Ln(ii) ions beyond C, N, and O first row main group donor atoms, the Ln(iii) terphenylthiolate iodides, LnIII(SAriPr6)2I (AriPr6= C6H3-2,6-(C6H2-2,4,6-iPr3)2, Ln = La, Nd) were reduced to LnII(SAriPr6)2complexes.

more » « less
Award ID(s):
Author(s) / Creator(s):
; ; ; ; ;
Publisher / Repository:
Royal Society of Chemistry
Date Published:
Journal Name:
Chemical Communications
Page Range / eLocation ID:
4601 to 4604
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    We present UV and/or optical observations and models of SN 2023ixf, a type II supernova (SN) located in Messier 101 at 6.9 Mpc. Early time (flash) spectroscopy of SN 2023ixf, obtained primarily at Lick Observatory, reveals emission lines of Hi, Hei/ii, Civ, and Niii/iv/vwith a narrow core and broad, symmetric wings arising from the photoionization of dense, close-in circumstellar material (CSM) located around the progenitor star prior to shock breakout. These electron-scattering broadened line profiles persist for ∼8 days with respect to first light, at which time Doppler broadened the features from the fastest SN ejecta form, suggesting a reduction in CSM density atr≳ 1015cm. The early time light curve of SN 2023ixf shows peak absolute magnitudes (e.g.,Mu= −18.6 mag,Mg= −18.4 mag) that are ≳2 mag brighter than typical type II SNe, this photometric boost also being consistent with the shock power supplied from CSM interaction. Comparison of SN 2023ixf to a grid of light-curve and multiepoch spectral models from the non-LTE radiative transfer codeCMFGENand the radiation-hydrodynamics codeHERACLESsuggests dense, solar-metallicity CSM confined tor= (0.5–1) × 1015cm, and a progenitor mass-loss rate ofṀ=102Myr−1. For the assumed progenitor wind velocity ofvw= 50 km s−1, this corresponds to enhanced mass loss (i.e.,superwindphase) during the last ∼3–6 yr before explosion.

    more » « less
  2. 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 LnB8species changes fromCstoC7vsymmetry accompanied by an oxidation-state change from +III to +I from the early to late lanthanides. All theC7v-LnB8clusters can be viewed as a monovalent Ln(I) coordinated by a η8-B82−doubly aromatic ligand. The B73−, B82−, and B9series 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.

    more » « less
  3. 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 (2P3/22P1/3) 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 ofMH I/M= 1.4 andMH I/Mbar,tot= 0.45. These results provide strong evidence for Hibeing the dominant baryonic matter component by mass in galaxies atz≈ 6.

    more » « less
  4. Abstract

    The synthesis of the first linear coordinated CuIIcomplex Cu{N(SiMe3)Dipp}2(1Dipp=C6H5‐2,6Pri2) and its CuIcounterpart [Cu{N(SiMe3)Dipp}2](2) is described. The formation of1proceeds through a dispersion force‐driven disproportionation, and is the reaction product of a CuIhalide and LiN(SiMe3)Dipp in a non‐donor solvent. The synthesis of2is accomplished by preventing the disproportionation into1by using the complexing agent 15‐crown‐5. EPR spectroscopy of1provides the first detailed study of a two‐coordinate transition‐metal complex indicating strong covalency in the Cu−N bonds.

    more » « less
  5. Abstract

    Exploration of the reduction chemistry of the 2,2’‐bipyridine (bipy) lanthanide metallocene complexes Cp*2LnCl(bipy) and Cp*2Ln(bipy) (Cp* = C5Me5) resulted in the isolation of a series of complexes with unusual composition and structure including complexes with a single Cp* ligand, multiple azide ligands, and bipy ligands with close parallel orientations. These results not only reveal new structural types, but they also show the diverse chemistry displayed by this redox‐active platform. Treatment of Cp*2NdCl(bipy) with excess KC8resulted in the formation of the mono‐Cp* Nd(III) complex, [K(crypt)]2[Cp*Nd(bipy)2],1, as well as [K(crypt)][Cp*2NdCl2],2, and the previously reported [K(crypt)][Cp*2Nd(bipy)]. A mono‐Cp* Lu(III) complex, Cp*Lu(bipy)2,3, was also found in an attempt to make Cp*2Lu(bipy) from LuCl3, 2 equiv. of KCp*, bipy, and K/KI. Surprisingly, the (bipy)1−ligands in neighboring molecules in the structure of3are oriented in a parallel fashion with intermolecular C⋅⋅⋅C distances of 3.289(4) Å, which are shorter than the sum of van der Waals radii of two carbon atoms, 3.4 Å. Another product with one Cp* ligand per lanthanide was isolated from the reaction of [K(crypt)][Cp*2Eu(bipy)] with azobenzene, which afforded the dimeric Eu(II) complex, [K(crypt)]2[Cp*Eu(THF)(PhNNPh)]2,4. Attempts to make4from the reaction between Cp*2Eu(THF)2and a reduced azobenzene anion generated instead the mixed‐valent Eu(III)/Eu(II) complex, [K(crypt)][Cp*Eu(THF)(PhNNPh)]2,5, which allows direct comparison with the bimetallic Eu(II) complex4. Mono‐Cp* complexes of Yb(III) are obtained from reactions of the Yb(II) complex, [K(crypt)][Cp*2Yb(bipy)], with trimethylsilylazide, which afforded the tetra‐azido [K(crypt)]2[Cp*Yb(N3)4],6, or the di‐azido complex [K(crypt)]2[Cp*Yb(N3)2(bipy)],7 a, depending on the reaction stoichiometry. A mono‐Cp* Yb(III) complex is also isolated from reaction of [K(crypt)][Cp*2Yb(bipy)] with elemental sulfur which forms the mixed polysulfido Yb(III) complex [K(crypt)]2[Cp*Yb(S4)(S5)],8 a. In contrast to these reactions that form mono‐Cp* products, reduction of Cp*2Yb(bipy) with 1 equiv. of KC8in the presence of 18‐crown‐6 resulted in the complete loss of Cp* ligands and the formation of [K(18‐c‐6)(THF)][Yb(bipy)4],9. The (bipy)1−ligands of9are arranged in a parallel orientation, as observed in the structure of3, except in this case this interaction is intramolecular and involves pairs of ligands bound to the same Yb atom. Attempts to reduce further the Sm(II) (bipy)1−complex, Cp*2Sm(bipy) with 2 equiv. of KC8in the presence of excess 18‐crown‐6 led to the isolation of a Sm(III) salt of (bipy)2−with an inverse sandwich Cp* counter‐cation and a co‐crystallized K(18‐c‐6)Cp* unit, [K2(18‐c‐6)2Cp*]2[Cp*2Sm(bipy)]2 ⋅ [K(18‐c‐6)Cp*],10.

    more » « less