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1. Dianionic Mononuclear Cyclo ‐P ₄ Complexes of Zero‐Valent Molybdenum: Coordination of the Cyclo ‐P ₄ Dianion in the Absence of Intramolecular Charge Transfer

   https://doi.org/10.1002/anie.201908885  

   Mandla, Kyle A.; Neville, Michael L.; Moore, Curtis E.; Rheingold, Arnold L.; Figueroa, Joshua S. (September 2019, Angewandte Chemie International Edition)

   Abstract Relative to other cyclic poly‐phosphorus species (that is,cyclo‐P_n), the planarcyclo‐P₄group is unique in its requirement of two additional electrons to achieve aromaticity. These electrons are supplied from one or more metal centers. However, the degree of charge transfer is dependent on the nature of the metal fragment. Unique examples of dianionic mononuclear η⁴‐P₄complexes are presented that can be viewed as the simple coordination of the [cyclo‐P₄]²⁻dianion to a neutral metal fragment. Treatment of the neutral, molybdenumcyclo‐P₄complexes Mo(η⁴‐P₄)I₂(CO)(CNAr^Dipp2)₂and Mo(η⁴‐P₄)(CO)₂(CNAr^Dipp2)₂with KC₈produces the dianionic, three‐legged piano stool complexes, [Mo(η⁴‐P₄)(CO)(CNAr^Dipp2)₂]²⁻and [Mo(η⁴‐P₄)(CO)₂(CNAr^Dipp2)]²⁻, respectively. Structural, spectroscopic, and computational studies reveal a similarity to the classic η⁶‐benzene complex (η⁶‐C₆H₆)Mo(CO)₃regarding the metal‐center valence state and electronic population of the planar‐cyclic ligand π system. 

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2. Ni ₂ P‐Modified Ta ₃ N ₅ and TaON for Photocatalytic Nitrate Reduction

   https://doi.org/10.1002/cnma.202000174  

   Wei, Lin; Adamson, Marquix_A_S; Vela, Javier (May 2020, ChemNanoMat)

   Abstract Self‐sustaining photocatalytic NO₃⁻reduction systems could become ideal NO₃⁻removal methods. Developing an efficient, highly active photocatalyst is the key to the photocatalytic reduction of NO₃⁻. In this work, we present the synthesis of Ni₂P‐modified Ta₃N₅(Ni₂P/Ta₃N₅), TaON (Ni₂P/TaON), and TiO₂(Ni₂P/TiO₂). Starting with a 2 mM (28 g/mL NO₃⁻−N) aqueous solution of NO₃⁻, as made Ni₂P/Ta₃N₅and Ni₂P/TaON display as high as 79% and 61% NO₃⁻conversion under 419 nm light within 12 h, which correspond to reaction rates per gram of 196 μmol g⁻¹ h⁻¹and 153 μmol g⁻¹ h⁻¹, respectively, and apparent quantum yields of 3–4%. Compared to 24% NO₃⁻conversion in Ni₂P/TiO₂, Ni₂P/Ta₃N₅and Ni₂P/TaON exhibit higher activities due to the visible light active semiconductor (SC) substrates Ta₃N₅and TaON. We also discuss two possible electron migration pathways in Ni₂P/semiconductor heterostructures. Our experimental results suggest one dominant electron migration pathway in these materials, namely: Photo‐generated electrons migrate from the semiconductor to co‐catalyst Ni₂P, and upshift its Fermi level. The higher Fermi level provides greater driving force and allows NO₃⁻reduction to occur on the Ni₂P surface. 

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3. Laser-cooling Cadmium Bosons and Fermions with Near Ultraviolet Triplet Excitations

   https://doi.org/10.1088/1742-6596/2889/1/012006  

   Gibble, Kurt (November 2024, Journal of Physics: Conference Series)

   Abstract Cadmium is laser-cooled and trapped with excitations to triplet states with UVA light, first using only the 67 kHz wide 326 nm intercombination line and subsequently, for large loading rates, the 25 MHz wide 361 nm³P₂→³D₃transition. Eschewing the hard UV 229 nm¹S₀→¹P₁transition, only small magnetic fields gradients, less than 6 G cm⁻¹, are required enabling a 100% transfer of atoms from the 361 nm trap to the 326 nm narrow-line trap. All 8 stable cadmium isotopes are straightforwardly trapped, including two nuclear-spin- $\frac{1}{2}$fermions that require no additional repumping. We observe evidence of³P₂collisions limiting the number of trapped metastable atoms, report isotope shifts for¹¹¹Cd and¹¹³Cd of the 326 nm¹S₀→³P₁, 480nm³P₁→³S₁, and 361 nm³P₂→³D₃transitions, and measure the¹¹⁴Cd 5s5p³P₂→ 5s5d³D₃transition frequency to be 830 096 573(15) MHz. 

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4. Mixed Signals From the Stable Isotope Composition of Precipitation and Plant Waxes in the Northern Tropical Andes

   https://doi.org/10.1029/2022JG006932  

   Pérez‐Angel, Lina C.; Sepúlveda, Julio; Montes, Camilo; Smith, Jamila J.; Molnar, Peter; González‐Arango, Catalina; Snell, Kathryn E.; Dildar, Nadia (December 2022, Journal of Geophysical Research: Biogeosciences)

   Abstract We evaluate the efficacy of the stable isotope composition of precipitation and plant waxes as proxies for paleoaltimetry and paleohydrology in the northern tropical Andes. We report monthly hydrogen (δ²H_p) and oxygen (δ¹⁸O_p) isotope values of precipitation for an annual cycle, and hydrogen isotope values of plant waxes (δ²H_wax) obtained from modern soils along the eastern and western flanks of the Eastern Cordillera of Colombia. δ²H_p, δ¹⁸O_p, as well as the unweighted mean δ²H_waxvalues ofn‐C₂₉,n‐C₃₁, andn‐C₃₃n‐alkanes in the eastern flank show a dependence on elevation (R² = 0.90, 0.82, and 0.65, respectively). In stark contrast, the stable isotope compositions of neither precipitation nor plant waxes from the western flank correlate with elevation (R² < 0.23), on top of a negligible (p‐value >0.05) correlation between δ²H_waxand δ²H_p. In general, δ²H_waxvalues along the eastern flank of the Eastern Cordillera seem to follow the trend of a simple Rayleigh distillation process that is consistent with studies elsewhere on the eastern side of the Andes in South America. Neither δ²H_pnor δ¹⁸O_p, and therefore δ²H_wax, offer reliable estimates of past elevations in the western flank, due perhaps to water vapor source mixing, evaporation overprint, contrasting plant communities, and/or differences in evapotranspiration. Thus, δ²H_waxis only reliable for paleohydrology and paleoaltimetry reconstructions on the eastern flank of the Andes, whereas interpretations based on δ²H_pand/or δ¹⁸O_pwest of the highest point of the Eastern Cordillera need to consider mixing of moisture sources in addition to precipitation amount. 

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5. Variability and Controls on δ ¹⁸ O, d‐excess, and ∆′ ¹⁷ O in Southern Peruvian Precipitation

   https://doi.org/10.1029/2020JD034009  

   Aron, Phoebe G.; Poulsen, Christopher J.; Fiorella, Richard P.; Levin, Naomi E.; Acosta, Rene P.; Yanites, Brian J.; Cassel, Elizabeth J. (December 2021, Journal of Geophysical Research: Atmospheres)

   Abstract The isotopic composition of precipitation is used to trace water cycling and climate change, but interpretations of the environmental information recorded in central Andean precipitation isotope ratios are hindered by a lack of multi‐year records, poor spatial distribution of observations, and a predominant focus on Rayleigh distillation. To better understand isotopic variability in central Andean precipitation, we present a three‐year record of semimonthly δ¹⁸O_pand δ²H_pvalues from 15 stations in southern Peru and triple oxygen isotope data, expressed as ∆′¹⁷O_p, from 32 precipitation samples. Consistent with previous work, we find that elevation correlates negatively with δ¹⁸O_pand that seasonal δ¹⁸O_pvariations are related to upstream rainout and local convection. Spatial δ¹⁸O_pvariations and atmospheric back trajectories show that both eastern‐ and western‐derived air masses bring precipitation to southern Peru. Seasonal d‐excess_pcycles record moisture recycling and relative humidity at remote moisture sources, and both d‐excess_pand ∆′¹⁷O_pclearly differentiate evaporated and non‐evaporated samples. These results begin to establish the natural range of unevaporated ∆′¹⁷O_pvalues in the central Andes and set the foundation for future paleoclimate and paleoaltimetry studies in the region. This study highlights the hydrologic understanding that comes from a combination of δ¹⁸O_p, d‐excess_p, and ∆′¹⁷O_pdata and helps identify the evaporation, recycling, and rainout processes that drive water cycling in the central Andes. 

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