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At least 487 records · Page 27

Can mesoscale models capture the effect from cluster wakes offshore?

Long wakes from offshore wind turbine clusters can extend tens of kilometers downstream, affecting the wind resource of a large area. Given the ability of mesoscale numerical weather prediction models to capture important atmospheric phenomena and mechanisms relevant to wake evolution, they are often used to simulate wakes behind large wind turbine clusters and their impact over a wider region. Yet, uncertainty persists regarding the accuracy of representing cluster wakes via mesoscale models and their wind turbine parameterizations. Here, we evaluate the accuracy of the Fitch wind farm parameterization in the Weather Research and Forecasting model in capturing cluster-wake effects using two different options to represent turbulent mixing in the planetary boundary layer. To this end, we compare operational data from an offshore wind farm in the North Sea that is fully or partially waked by an upstream array against high-resolution mesoscale simulations. In general, we find that mesoscale models accurately represent the effect of cluster wakes on front-row turbines of a downstream wind farm. However, the same models may not accurately capture cluster-wake effects on an entire downstream wind farm, due to misrepresenting internal-wake effects.

17 WIND ENERGY↗

An Intelligent Adaptable Monitoring Package. Final Report

The “Intelligent Adaptable Monitoring Package” project was a four-year effort that demonstrated the feasibility of integrated sensing packages at tidal and wave energy sites. Such integration is generally required by the breadth of sensors required to understand environmental effects at marine energy sites and the operational difficulty of deploying, maintaining, and recovering such sensors. Over the course of the project, the Adaptable Monitoring Package (AMP) was deployed in multiple settings, each corresponding to a project budget period: - Budget Period 1: Demonstration of cabled deployment at Pacific Northwest National Laboratory’s Marine Science Laboratory. The deployment highlighted AMP hardware endurance over a 4-month deployment in a tidally-dominated environment and laid the groundwork for machine learning algorithms to detect and classify targets present in active sonar data. - Budget Period 2: Demonstration of an autonomous deployment at PacWave South off the coast of Newport, Oregon. The deployment highlighted the stability of AMP hardware and software, with the autonomous package collecting data on a duty cycle over a 1.5-month deployment. - Budget Period 3: Demonstration of an autonomous deployment powered by a wave energy converter at the U.S. Navy’s Wave Energy Test Site. The deployment highlighted the potential of wave energy to power ocean observatories and led to the development of machine learning algorithms to detect and classify targets in optical camera data. In aggregate, this project’s greatest success was demonstrating the AMP’s flexibility in a range of deployment scenarios. Each budget period represented a “first of a kind” demonstration of integrated instrumentation – cabled AMP, autonomous AMP, wave-energy powered AMP – and each deployment helped to identify and set goals for the next. Further, despite the exploratory nature of these deployments, each one achieved high system up-time and proved that flexible integration of multiple sensors in a single package represents a viable strategy for marine energy environmental monitoring. The key lessons learned from the project are: - Without continuous power, either from a shore cable or in situ source, many of the benefits of integration are lost (If continuous power is not available, the ability to detect rare events is lost, as is the ability to minimize the risk of behavioral changes through adaptive sensing. However, even on a duty cycle, there is still value in being able to acquire synchronous data from multiple sensors.); and - Observations from a moving platform present substantially greater data processing challenges than those from stationary platforms. Finally, these deployments also demonstrate an important truth: successful integration alone does not guarantee that relevant data are collected. To grow the knowledge base about environmental interactions with marine energy converters, integrated systems, like the AMP, need to include the right sensor mix and connect the data pipelines to effective processing algorithms. These deployments establish a strong foundation for future collaborations with the environmental research community: not only to understand the environmental effects of marine energy, but also to improve our general ability to study life in the sea.

16 TIDAL AND WAVE POWER↗

Establishing charge-transfer excitons in 2D perovskite heterostructures

Charge-transfer excitons (CTEs) immensely enrich property-tuning capabilities of semiconducting materials. However, such concept has been remaining as unexplored topic within halide perovskite structures. Here, we report that CTEs can be effectively formed in heterostructured 2D perovskites prepared by mixing PEA 2 PbI 4 :PEA 2 SnI 4 , functioning as host and guest components. Remarkably, a broad emission can be demonstrated with quick formation of 3 ps but prolonged lifetime of ~0.5 μs. This broad PL presents the hypothesis of CTEs, verified by the exclusion of lattice distortion and doping effects through demonstrating double-layered PEA 2 PbI 4 /PEA 2 SnI 4 heterostructure when shearing-away PEA 2 SnI 4 film onto the surface of PEA 2 PbI 4 film by using hand-finger pressing method. The below-bandgap photocurrent indicates that CTEs are vital states formed at PEA 2 PbI 4 :PEA 2 SnI 4 interfaces in 2D perovskite heterostructures. Electroluminescence shows that CTEs can be directly formed with electrically injected carriers in perovskite LEDs. Clearly, the CTEs presents a new mechanism to advance the multifunctionalities in 2D perovskites.

36 MATERIALS SCIENCE↗

Convergence of Cloud Droplet Spectral Relative Dispersion During Entrainment‐Mixing Based on Particle‐Resolved Direct Numerical Simulations

Entrainment-mixing processes critically impact cloud microphysical properties, but their effects on the relative dispersion (d) of cloud droplet size distributions (CDSDs) remain elusive. A direct numerical simulation model is initialized with different CDSDs to fill the gap. These results show that d decreases for broad CDSDs and increases for narrow ones, ultimately converging to approximately 0.5 regardless of initial CDSDs during the evaporation-dominated mixing stage. The supersaturation fluctuation and the shape of CDSDs jointly influence the convergence behavior of d. Further sensitivity tests show that the initial microphysical/dynamical/thermodynamical conditions exert negligible effects on the final converged value of d but affect the convergence rate (k). The k generally increases with increasing droplet number concentration and dissipation rate, and increases with decreasing liquid water content, relative humidity of entrained air, and mixing fraction of cloudy air. A conceptual model with two timescales is proposed; k and the timescales are negatively correlated, meaning that slow mixing and/or evaporation process results in slow convergence of d. In conclusion, this finding provides an important reference for improving understanding and parameterization of d during the entrainment-mixing processes.

54 ENVIRONMENTAL SCIENCES↗

Target Configuration Effect on Microstructures and Properties of Vertically Aligned Nanocomposites

Vertically aligned nanocomposites (VANs) are unique thin films with vertical nanostructures embedded in a matrix material, allowing for the integration of two distinct materials. These nanocomposites offer novel combined physical properties, such as nanocomposite-based multiferroics and strongly coupled physical properties, such as magneto-optic coupling. Much work has been conducted in exploring different two-phase combinations and various processing conditions to achieve novel tunable properties that cannot be obtained by any single-phase material alone. Here, in this work, the target configuration effects are explored for the growth of LaFeO 3 –CoNi 2 O 4 VANs. Both mixed and pie-shaped targets are utilized to compare the target configuration effects on the phase separation, morphology tuning, and their resulting physical properties, including optical and magnetic properties. This work suggests that the target configuration is another important parameter for achieving the desired VAN morphology and can be used to design different two-phase VANs with tailorable properties.

36 MATERIALS SCIENCE↗

Estimating the Meridional Extent of Adiabatic Mixing in the Stratosphere Using Age-Of-Air

Wave-induced adiabatic mixing in the winter midlatitudes is one of the key processes impacting stratospheric transport. Understanding its strength and structure is vital to understanding the distribution of trace gases and their modulation under a changing climate. Age-of-air is often used to understand stratospheric transport, and this study proposes refinements to the vertical age gradient theory of Linz et al. (2021), https://doi.org/10.1029/2021JD035199. The theory assumes exchange of air between a well-mixed tropics and a well-mixed extratropics, separated by a transport barrier, quantifying the adiabatic mixing flux across the interface using age-based measures. These assumptions are re-evaluated and a refined framework that includes the effects of meridional tracer gradients is established to quantify the mixing flux. This is achieved, in part, by computing a circulation streamfunction in age-potential temperature coordinates to generate a complete distribution of parcel ages being mixed in the midlatitudes. The streamfunction quantifies the “true” age of parcels mixed between the tropics and the extratropics. Applying the revised theory to an idealized and a comprehensive climate model reveals that ignoring the meridional gradients in age leads to an underestimation of the wave-driven mixing flux. Stronger, and qualitatively similar fluxes are obtained in both models, especially in the lower-to-middle stratosphere. While the meridional span of adiabatic mixing in the two models exhibits some differences, they show that the deep tropical pipe, that is, latitudes equatorward of 15° barely mix with older midlatitude air. The novel age-potential temperature circulation can be used to quantify additional aspects of stratospheric transport.

54 ENVIRONMENTAL SCIENCES↗

The Influence of Alkyl Spacers and Molecular Weight on the Charge Transport and Storage Properties of Oxy‐Bithiophene‐Based Conjugated Polymers

Abstract Conjugated polymers (CPs) with polar side chains can conduct electronic and ionic charges simultaneously, making them promising for bioelectronics, electrocatalysis and energy storage. Recent work showed that adding alkyl spacers between CP backbones and polar side chains improved electronic charge carrier mobility, reduced swelling and enhanced stability, without compromising ion transport. However, how alkyl spacers impact polymer backbone conformation and, subsequently, electronic properties remain unclear. In this work, we design two oxy‐bithiophene‐based CP series, each featuring progressively extended alkyl spacer lengths and two distinct molecular weight (MW) distributions. Using operando characterisations, we evaluate the (spectro)electrochemical and swelling properties of the polymer thin films, and their performance in organic field‐effect transistors and organic electrochemical transistors. Surprisingly, alkyl spacers negatively impact the hole mobility of our polymers, with higher MW amplifying this effect. Using molecular dynamics simulations, we show that it is thermodynamically favourable for adjacent non‐polar alkyl spacers to aggregate in polar electrolytes, leading to backbone twisting. Further spectroscopic measurements corroborate this prediction. Our findings demonstrate the active interactions between side chain structure, MW and electrolyte/solvent polarity in influencing polymer performance, underscoring the importance of considering solvation environment effects on polymer conformation when designing new mixed conducting CPs for electrochemical applications.

Yu, Hang [Department of Physics and Centre for Pro↗

The Influence of Alkyl Spacers and Molecular Weight on the Charge Transport and Storage Properties of Oxy‐Bithiophene‐Based Conjugated Polymers

Conjugated polymers (CPs) with polar side chains can conduct electronic and ionic charges simultaneously, making them promising for bioelectronics, electrocatalysis and energy storage. Recent work showed that adding alkyl spacers between CP backbones and polar side chains improved electronic charge carrier mobility, reduced swelling and enhanced stability, without compromising ion transport. However, how alkyl spacers impact polymer backbone conformation and, subsequently, electronic properties remain unclear. In this work, we design two oxy-bithiophene-based CP series, each featuring progressively extended alkyl spacer lengths and two distinct molecular weight (MW) distributions. Using operando characterisations, we evaluate the (spectro)electrochemical and swelling properties of the polymer thin films, and their performance in organic field-effect transistors and organic electrochemical transistors. Surprisingly, alkyl spacers negatively impact the hole mobility of our polymers, with higher MW amplifying this effect. Using molecular dynamics simulations, we show that it is thermodynamically favourable for adjacent non-polar alkyl spacers to aggregate in polar electrolytes, leading to backbone twisting. Further spectroscopic measurements corroborate this prediction. Our findings demonstrate the active interactions between side chain structure, MW and electrolyte/solvent polarity in influencing polymer performance, underscoring the importance of considering solvation environment effects on polymer conformation when designing new mixed conducting CPs for electrochemical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Diazo Linker Ligand Promotes Flexibility and Induced Fit Binding in a Microporous Copper Coordination Network

Abstract Flexible organic linkers represent an intuitive and effective strategy to design flexible metal–organic materials. We report herein a systematic study concerning the effect of varying the central bond of mixed pyridyl‐benzoate linkers, L, upon the flexibility of three isostructuralkddtopology microporous coordination networks (CNs) of formula ML 2 :X‐kdd‐1‐Cu,1= L = (E)‐4‐(pyridin‐4‐yldiazenyl)benzoate;X‐kdd‐2‐Cu,2= L = (E)‐4‐(2‐(pyridin‐4‐yl)vinyl)benzoate; the previously reportedX‐kdd‐3‐Cu,3= L = 4‐(pyridin‐4‐ylethynyl)benzoate. As revealed by single crystal x‐ray diffraction (SCXRD) and gas sorption studies,X‐kdd‐1‐Cu, exhibited gate‐opening during CO 2 and hydrocarbon (C2 and C8) sorption experiments whereas the other two CNs did not. Insight into these phase transformations was gained from in situ variable‐pressure and variable temperature powder X‐ray diffraction (PXRD), SCXRD, and modeling. Rotation of ligand1around the diazo bond, torsion angle changes between phenyl and carboxylate moieties, and deformation of the Cu‐based rod building blocks enabled activatedX‐kdd‐1‐Cuto form new phases with C8 isomers and CH 2 Cl 2 , CH 2 Cl 2 inducing contraction of the activated phase. Computational studies suggest that1enables flexibility thanks to its lower barrier of deformation versus2or3. This study teaches that diazo moieties could offer a general strategy to enhance the flexibility of CNs.

Chemistry↗

The genetic basis for panicle trait variation in switchgrass ( Panicum virgatum )

Grass species exhibit large diversity in panicle architecture influenced by genes, the environment, and their interaction. The genetic study of panicle architecture in perennial grasses is limited. In this study, we evaluate the genetic basis of panicle architecture including panicle length, primary branching number, and secondary branching number in an outcrossed switchgrass QTL population grown across ten field sites in the central USA through multi-environment mixed QTL analysis. We also evaluate genetic effects in a diversity panel of switchgrass grown at three of the ten field sites using genome-wide association (GWAS) and multivariate adaptive shrinkage. Furthermore, we search for candidate genes underlying panicle traits in both of these independent mapping populations. Overall, 18 QTL were detected in the QTL mapping population for the three panicle traits, and 146 unlinked genomic regions in the diversity panel affected one or more panicle trait. Twelve of the QTL exhibited consistent effects (i.e., no QTL by environment interactions or no QTL × E), and most (four of six) of the effects with QTL × E exhibited site-specific effects. Most (59.3%) significant partially linked diversity panel SNPs had significant effects in all panicle traits and all field sites and showed pervasive pleiotropy and limited environment interactions. Panicle QTL co-localized with significant SNPs found using GWAS, providing additional power to distinguish between true and false associations in the diversity panel.

59 BASIC BIOLOGICAL SCIENCES↗

Corrosion Behavior of a Reactive Bond Between Stainless Steel and a Cast AlCeMg Alloy

Corrosion is a longstanding issue for metal components, especially those used in heat exchanger applications. Al–Ce–Mg alloys may provide a potential solution to this problem due to their good mechanical properties and potential reaction bonding with other metals. The reaction bonding involves a “reactive” bond that occurs upon casting of Al–Ce–Mg alloy over stainless steel (SS). Here this study examined the corrosion response of Al–2Ce–6Mg (atomic percent)/(SS) reactive bond interfaces after samples were completely submerged in nitric, sulfuric, formic, and mixed acids for 267 h. Scanning electron microscopy revealed that in the as-cut condition, reactive bond formations were seen frequently throughout the length of the casting and maintained a secure bond between the alloy and the SS tubes. Furthermore, the nitric, sulfuric, and the mixed acids did not have a deleterious effect on the reactive bond structure. However, formic acid did produce changes in both the microstructural appearance and the elemental profile across the bond due to the formation of corrosion reaction products on the acid-exposed surface.

36 MATERIALS SCIENCE↗

Impact of molten salt inflow on the temperature distribution in thermal energy storage tanks at startup for central receiver concentrating solar power plants

Concentrating Solar Power (CSP) systems with molten salt thermal energy storage (TES) tanks are one of the most promising, renewable-based energy conversion technologies for larger-scale power generation. The TES tank is one of the most critical components in CSP plants due to its high-temperature operation (up to 565 °C), daily thermal cycling, and intermittent solar radiation conditions. The plant startup is one of the most challenging operation conditions that could lead to damaging thermal gradients due to low salt inventory levels. In this study an analytical model for the sparger ring was developed and integrated with a detailed computational fluid dynamics model of a commercial-scaled molten salt tank. The integrated model allows an accurate representation of the tank operation to evaluate the effect of molten salt inflow on the mixing process. The tank filling process during plant startup was analyzed considering sparger rings with variations in design features, including inlet orifice configurations, number of orifices, direction of the inlets, and orifice diameter. The results demonstrated that higher temperature gradients are obtained in the tank floor during the plant startup. A sparger ring configuration with a predetermined orifice inlet inclination (30°, 45° and 60°) leads to significant temperature differences in the floor, between 57 °C and 62 °C, but better homogeneity in the temperature of the salt inventory. Lower salt inflow velocities result in a more homogeneous floor temperature, with maximum temperature differences under 38 °C. The sparger ring configuration with 52 orifices of 1-in. diameter and vertical flow showed better homogeneity in the temperature differences as a function of the salt level and lower temperature gradients in the tank floor. Because large temperature gradients in the tank's floor have been identified as one of the main factors contributing to tank failures, assessing various sparger ring design features is fundamental to determining proper inflow conditions that lead to low-temperature gradients and reducing failure susceptibility.

14 SOLAR ENERGY↗

Characterization of the indoor near-field aerosol transmission in a model commercial office building

To evaluate the exposure potential of infectious aerosols containing SARS-CoV-2 in an office building setting, synthetic test aerosols were used to experimental study airborne particle transmission in a multizone small office test building at the Oak Ridge National Laboratory. Nine measurement points in a single zone using active aerosol impactors report that the coefficient of variation of the time-averaged concentration is <10% in two campaigns and < 15% in one campaign, so a nearly well-mixed condition was noted. To understand the effect of HVAC system operation on the dynamic concentration of aerosols in office spaces, an aerosol transport model that includes factors such as outside air (OA) ratio, filtration, return air fraction, transport loss in air ducts, and particle deposition has been developed. The results of model fitting demonstrate strong agreement with experimental data. Overall, our investigation finds the return air fraction effects outweigh other mechanisms for the aerosol recirculation in this study, and the impact of air change rate (ACR) is more important than the small particle deposition for aerosol removal. Because ACR dominates the aerosol transport, the full model can be simplified to just one factor, the ACR, while maintaining an acceptable representation of the experimental data.

60 APPLIED LIFE SCIENCES↗

Polyacrylonitrile-based electrolytes: How processing and residual solvent affect ion transport and stability

Polyacrylonitrile (PAN) is one of the alternative candidate polymer hosts to form solid polymer electrolytes (SPEs) besides the widely used poly(ethylene oxide). In this study, we systematically investigate the processing of PAN based SPEs containing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, using dimethylformamide (DMF) as the solvent. The effects of PAN processing procedure including solution mixing, casting, and drying on the morphology, ion transport, solvation structure, Li and oxidative stability of PAN electrolytes are thoroughly examined. In particular, four drying conditions are investigated and the amount of residual DMF is accurately determined using infrared (IR) spectroscopy. Varying the drying conditions can lead to five orders of magnitude decrease in the ionic conductivity. As DMF content decreases, the SPE's stability again Li metal dramatically improves. The practical oxidative stability is also strongly affected by the residual DMF content, ranging from 2.5 V to 3.5 V, much lower than reported values. Finally, the role of the residual DMF solvent is elucidated. DMF content vitally influences ion solvation structure at different concentration regimes, which ultimately dictates the ion conduction mechanism and oxidative stability of PAN based SPEs. In conclusion, this thorough study lays the groundwork for future development of PAN based electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Reduction Pathways from Goethite to Green Iron in Alkaline Solution with Silicate Additive

Energy-efficient and low-temperature iron electrolysis in alkaline solutions is a low-cost and sustainable ironmaking process with zero-carbon emissions when renewable electrical sources are involved. However, its implementation is hindered by electrochemically inert Fe 3 O 4 and parasitic H 2 gas formation during the electrochemical reduction process, resulting in the low energy efficiency of iron electrolysis. Here, we further explore the potential of electrochemical reduction of goethite (FeOOH) by employing a low concentration of silicate additive in an alkaline solution to mitigate Fe 3 O 4 accumulation and H 2 generation. Electrochemical measurements coupled with operando X-ray diffraction and X-ray absorption spectroscopy suggested FeOOH → Fe 3 O 4 → Fe(OH) 2 → Fe reduction pathways. Interestingly, a poorly crystalline or amorphous Fe(OH) 2 phase formed in the NaOH/silicate mixed electrolyte, possibly due to the inhibitive effect of silicate on water and ion transport, which eventually contributed to the improved reduction of Fe 3 O 4 , also supported by atomistic simulations. This work demonstrates the potential for silicate as a low-cost and effective electrolyte additive to improve room-temperature green iron formation via electrolysis.

36 MATERIALS SCIENCE↗

Universal Approach for the Depolymerization of Polyamides via Photothermal Conversion

Polyamides (PAs) exhibit excellent chemical stability and mechanical resistance, yet these same characteristics lead to their widespread accumulation in the environment as pollution. In this work, we developed an inclusive and operationally simple photothermal strategy to recycle PAs, overcoming the high energy barriers necessary to break down these materials. PAs can be depolymerized using photothermally mediated ring-closing depolymerization and acidic hydrolysis to afford cyclic and linear monomers using carbon black as a photothermal agent (PTA) under visible light irradiation. We showed that polyamide 6 is efficiently depolymerized to ε-caprolactam with 74% yield in 10 min. Similarly, in 1 h, the photothermal acidic hydrolysis of polyamide 6,6 afforded hexamethylene diamine and adipic acid with 97 and 96% yields, respectively. This method was further applied to a variety of aliphatic and aromatic PAs and mixed PA waste. Both photothermally promoted processes effectively depolymerize pigment-containing postconsumer waste by leveraging existing black pigments as PTAs. Here, photothermal conversion provided a general and rapid route for PA depolymerization under visible light irradiation, enabling high monomer yields with inexpensive reagents and a general tolerance to additives, demonstrating this approach’s potential for a circular plastic economy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mangrove peat and algae leachates elicit rapid and contrasting molecular and microbial responses in coastal waters

Abstract As sea level rises, previously sequestered blue carbon can be exported offshore as particulate or dissolved organic matter where it may be re-mineralized or sequestered. The priming effect, or interactive effects of organic matter turnover with a mixed substrate, is well described in soils, but still debated in aquatic systems. Priming may contribute to enhanced blue carbon re-mineralization in coastal environments. Here we examined mangrove-derived dissolved organic matter turnover in a lab incubation, with leachates from mangrove peat, 13 C-labeled algae, and peat+algae (primed). Particulate and dissolved organic matter were assessed; microbial metatranscriptomes were evaluated; and dissolved organic matter was characterized with high resolution mass spectrometry. Stable isotopes indicated rapid allocation of algal-derived dissolved organic matter into particulate organic matter. The algal treatment had the greatest increase in carbon dioxide, but primed and peat treatments had the greatest loss of dissolved organic carbon, greater RNA concentrations, and similar changes in total carbon dioxide. This suggests that, while total carbon dioxide did not increase under priming conditions, the addition of a peat substrate may promote microbial biomass production relative to carbon dioxide production. This work highlights that more targeted studies investigating the specific mechanisms of priming are necessary to address the molecular and microbial transformations associated with priming in aquatic systems.

54 ENVIRONMENTAL SCIENCES↗

The striking influence of oxophilicity differences in heterometallic Mo–Mn oxide cluster reactions with water

Mixed-metal oxides have proven to be effective catalysts for the hydrogen evolution reaction, often outperforming either of the binary metal oxides. The reactivity of Mn x MoO y - (x = 1, 2; y = 3, 4) clusters toward H 2 O was investigated via time-of-flight mass spectrometry with clear evidence of cluster oxidation and corresponding H 2 production, specifically for Mn x MoO 3 - (x = 1, 2) clusters. Unlike previously studied MoxOy- clusters, which assumed a broad distribution of stoichiometries (typically x ≤ y ≤ 3x), both MnMoOy- and Mn 2 MoO y - preferentially formed y = 3 and 4 compositions in significant quantities under our source conditions. The electronic and molecular structures of the Mn x MoO y (x = 1, 2; y = 3, 4) anion and neutral clusters were probed with anion photoelectron spectroscopy and analyzed with supporting density functional theory calculations. Our studies suggest that both metal centers are involved in initial cluster–water complex formation, while Mo is the center that undergoes oxidation; hence, reactivity terminates when Mo is saturated in its highest oxidation state of +6. Across these four clusters, Mn remains relatively reduced and is stable in a high-spin electronic configuration. The preferential reactivity of water molecules toward the Mo center rather than Mn is rationalized by the much lower relative oxophilicity of Mn.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗