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1. Distinct Bimetallic Cooperativity Among Water Reduction Catalysts Containing [Co ^III Co ^III ], [Ni ^II Ni ^II ], and [Zn ^II Zn ^II ] Cores

   https://doi.org/10.1002/chem.202104426  

   Morgan, Fredricka; Schaugaard, Richard; Anderson, Dennis; Schlegel, H_Bernhard; Verani, Cláudio_N (March 2022, Chemistry – A European Journal)

   Abstract Three binuclear species [LCo^III₂(μ‐Pz)₂](ClO₄)₃(1), [LNi^II₂(CH₃OH)₂Cl₂]ClO₄(2), and [LZn^II₂Cl₂]PF₆(3) supported by the deprotonated form of the ligand 2,6‐bis[bis(2‐pyridylmethyl) amino‐methyl]‐4‐methylphenol were synthesized, structurally characterized as solids and in solution, and had their electrochemical and spectroscopic behavior established. Species1–3had their water reduction ability studied aiming to interrogate the possible cooperative catalytic activity between two neighboring metal centers. Species1and2reduced H₂O to H₂effectively at an applied potential of −1.6 V_Ag/AgCl, yielding turnover numbers of 2,820 and 2,290, respectively, after 30 minutes. Species3lacked activity and was used as a negative control to eliminate the possibility of ligand‐based catalysis. Pre‐ and post‐catalytic data gave evidence of the molecular nature of the process within the timeframe of the experiments. Species1showed structural, rather than electronic cooperativity, while species2displayed no obvious cooperativity. DFT methods complemented the experimental results determining plausible mechanisms. 

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2. Spectroscopic study of the 4f ⁷ 6s ^{2 8} S 7/2∘ – 4f ⁷ ( ⁸ S ^° ) 6s6p( ¹ P ^° ) ⁸ P _5/2,7/2 transitions in neutral europium-151 and europium-153: absolute frequency and hyperfine structure

   https://doi.org/10.1364/JOSAB.521181  

   Maruko, C.; Çölmek, N_N; Herd, M_T; Ahrendsen, K_J; Cabrales, B.; Cannon, G.; Davis, E.; Guo, X_Y; Karani, T.; Wallace, A.; et al (April 2024, Journal of the Optical Society of America B)

   We report on spectroscopic measurements on the 4f⁷6s²⁸S_7/2^∘−4f⁷(⁸S^∘)6s6p(¹P^∘)⁸P_5/2,7/2transitions at 466.32 nm and 462.85 nm, respectively, in neutral europium-151 and europium-153. The center of gravity frequencies for the 151 and 153 isotopes for both transitions are reported for the first time using saturated absorption spectroscopy. For the 6s6p(¹P^∘)⁸P_5/2state, the center of gravity frequencies were found to be 642,894,493.3(4) MHz and 642,891,693.3(9) MHz for the 151 and 153 isotopes, respectively. The hyperfine constants for the upper state were found to beA(151)=−157.01(3)MHz,B(151)=74.5(4)MHz andA(153)=−69.43(14)MHz,B(153)=191.0(26)MHz. These hyperfine values are all consistent with previously published results except forB(151) that has a small discrepancy. The isotope shift was found to be 2799.54(20) MHz, a small discrepancy with previously published results. For the 6s6p(¹P^∘)⁸P_7/2state, the center of gravity frequencies were found to be 647,708,930.6(6) MHz and 647,705,958.4(26) MHz for the 151 and 153 isotopes, respectively. The hyperfine constants for the upper state were found to beA(151)=−218.66(4)MHz,B(151)=−293.4(8)MHz andA(153)=−97.15(13)MHz,B(153)=−750(3)MHz. These values are all consistent with previously published results except forA(151) that has a small discrepancy. The isotope shift was found to be 2972.8(5) MHz, a small discrepancy with previously measured results. 

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3. Phosphorescence in Mn ⁴⁺ -Doped R ⁺ / R ²⁺ Germanates ( R ⁺ = Na ⁺ or K ⁺ , R ²⁺ = Sr ²⁺ )

   https://doi.org/10.1021/acs.inorgchem.2c01364  

   Novikov, Sergei A.; Lu, Yimin; Zhang, Weiguo; Halasyamani, P. Shiv; Hariyani, Shruti; Brgoch, Jakoah; Klepov, Vladislav V.; zur Loye, Hans-Conrad; Mozharivskyj, Yurij (June 2022, Inorganic Chemistry)
4. Encapsulation of tricopper cluster in a synthetic cryptand enables facile redox processes from Cu ^I Cu ^I Cu ^I to Cu ^II Cu ^II Cu ^II states

   https://doi.org/10.1039/D0SC05441K  

   Zhang, Weiyao; Moore, Curtis E.; Zhang, Shiyu (March 2021, Chemical Science)

   null (Ed.)

   One-pot reaction of tris(2-aminoethyl)amine (TREN), [Cu I (MeCN) 4 ]PF 6 , and paraformaldehyde affords a mixed-valent [ TREN4 Cu II Cu I Cu I (μ 3 -OH)](PF 6 ) 3 complex. The macrocyclic azacryptand TREN4 contains four TREN motifs, three of which provide a bowl-shape binding pocket for the [Cu 3 (μ 3 -OH)] 3+ core. The fourth TREN caps on top of the tricopper cluster to form a cryptand, imposing conformational constraints and preventing solvent interaction. Contrasting the limited redox capability of synthetic tricopper complexes reported so far, [ TREN4 Cu II Cu I Cu I (μ 3 -OH)](PF 6 ) 3 exhibits several reversible single-electron redox events. The distinct electrochemical behaviors of [ TREN4 Cu II Cu I Cu I (μ 3 -OH)](PF 6 ) 3 and its solvent-exposed analog [ TREN3 Cu II Cu II Cu II (μ 3 -O)](PF 6 ) 4 suggest that isolation of tricopper core in a cryptand enables facile electron transfer, allowing potential application of synthetic tricopper complexes as redox catalysts. Indeed, the fully reduced [ TREN4 Cu I Cu I Cu I (μ 3 -OH)](PF 6 ) 2 can reduce O 2 under acidic conditions. The geometric constraints provided by the cryptand are reminiscent of Nature's multicopper oxidases (MCOs). For the first time, a synthetic tricopper cluster was isolated and fully characterized at Cu I Cu I Cu I ( 4a ), Cu II Cu I Cu I ( 4b ), and Cu II Cu II Cu I ( 4c ) states, providing structural and spectroscopic models for many intermediates in MCOs. Fast electron transfer rates (10 5 to 10 6 M −1 s −1 ) were observed for both Cu I Cu I Cu I /Cu II Cu I Cu I and Cu II Cu I Cu I /Cu II Cu II Cu I redox couples, approaching the rapid electron transfer rates of copper sites in MCO. 

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5. Fine-structure Transitions of Ne ⁺ , Ar ⁺ , Ne ²⁺ , and Ar ²⁺ Induced by Collisions with Atomic Hydrogen

   https://doi.org/10.3847/1538-4357/ad0e77  

   Yan, Pei-Gen; Babb, James F (January 2024, The Astrophysical Journal)

   Abstract We calculate cross sections for fine-structure transitions of Ne⁺, Ar⁺, Ne²⁺, and Ar²⁺in collisions with atomic hydrogen by using quantum-mechanical methods. Relaxation rate coefficients are calculated for temperatures up to 10,000 K. The temperature-dependent critical densities for the relaxation of Ne⁺, Ar⁺, Ne²⁺, and Ar²⁺in collisions with H have been determined and compared to the critical densities for collisions with electrons. The present calculations will be useful for studies utilizing the infrared lines [Neii] 12.8, [Neiii] 15.6, [Neiii] 36.0, [Arii] 6.99, [Ariii] 8.99, and [Ariii] 21.8μm as diagnostics of, for example, planetary nebulae and star formation. 

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