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A review of privacy in energy applications

As the distribution system continues to experience an increase in distributed energy resource (DER) and electric vehicle (EV) penetration, so does the need for new solutions that can help grid operators manage and leverage their capabilities. This will undoubtedly lead to new operational schemes and business opportunities that will transform the traditional consumer into a prosumer who will be more actively engaged in grid operations. Although the field is still under active development, many of the potential use cases presented in literature or industry are built upon edge computing, two-way communications, and other innovative computational constructs to attain their goals. However, at their core, many use cases assume a great level of data access to aid with the decision-making process, an assumption that may need to be revised to ensure fair and equitable operational processes are maintained. This may be particularly true as edge resources are predicted to participate in retail-side, many-to-many, or peer-to-peer markets and thus may lead to financial impacts if data access considerations are ignored. The need to revise data access mechanisms can be further justified by the introduction of new participants into the operational process, who do not have the same level of trust, nor the incentives to focus on energy delivery as their primary objective. At the same time, more consumers are becoming aware of their own data, and the potential impacts of its abuse. To help solution developers better understand these risks, this report has been developed to offer an initial introduction to the topic of privacy. This is achieved by 1) Highlighting the need for privacy-aware solutions; 2) Encouraging system designers to be inquisitive about the status quo; 3) Documenting the existing threat space; 4) Presenting and evaluating tools that may be helpful towards enabling better privacy postures; and 5) Making recommendations to encourage the adoption of better practices. From a technical perspective, the report focuses on evaluating two potential techniques by applying them to the Transactive Energy Space. Based on the obtained results, it can be established that differential privacy (DP) methods may have limited applicability when highly correlated, time-series data records need to be protected. However, DP may be a powerful tool when it is used to aggregate and analyze mid-size and large-size data sets in a more traditional statistical environment. The second tool under evaluation is threshold cryptography, which can guarantee complete secrecy (and thus privacy) but requires the establishment of key management procedures and dedicated communication channels for key coordination. Therefore, due to its increased computational overhead, the use of threshold cryptography must be weighted using a cost/benefit analysis on a per-application basis.

24 POWER TRANSMISSION AND DISTRIBUTION↗

The E3SM Diagnostics Package (E3SM Diags v2.7): a Python-based diagnostics package for Earth system model evaluation

Abstract. The E3SM Diagnostics Package (E3SM Diags) is a modern, Python-based Earth system model (ESM) evaluation tool (with Python module name e3sm_diags), developed to support the Department of Energy (DOE) Energy Exascale Earth System Model (E3SM). E3SM Diags provides a wide suite of tools for evaluating native E3SM output, as well as ESM data on regular latitude–longitude grids, including output from Coupled Model Intercomparison Project (CMIP) class models. E3SM Diags is modeled after the National Center for Atmospheric Research (NCAR) Atmosphere Model Working Group (AMWG, 2022) diagnostics package. In its version 1 release, E3SM Diags included a set of core essential diagnostics to evaluate the mean physical climate from model simulations. As of version 2.7, more process-oriented and phenomenon-based evaluation diagnostics have been implemented, such as analysis of the quasi-biennial oscillation (QBO), the El Niño–Southern Oscillation (ENSO), streamflow, the diurnal cycle of precipitation, tropical cyclones, ozone and aerosol properties. An in situ dataset from DOE's Atmospheric Radiation Measurement (ARM) program has been integrated into the package for evaluating the representation of simulated cloud and precipitation processes. This tool is designed with enough flexibility to allow for the addition of new observational datasets and new diagnostic algorithms. Additional features include customizable figures; streamlined installation, configuration and execution; and multiprocessing for fast computation. The package uses an up-to-date observational data repository maintained by its developers, where recent datasets are added to the repository as they become available. Finally, several applications for the E3SM Diags module were introduced to fit a diverse set of use cases from the scientific community.

54 ENVIRONMENTAL SCIENCES↗

Preliminary HEA Solid Phase Processing Development Report

The development of high temperature fuel cladding materials to withstand a variety of extreme environments have received much attention. Several potential materials systems that have been identified for the fuel systems and core structural materials application in advanced reactor systems are ferritic/martensitic steel (e.g., HT9), austenitic stainless steels (e.g., 316 LN), oxide-dispersion strengthened steels (e.g., 12 YWT), Ni-based alloys and ceramic-based composites depending on the type of the reactors. Though these material systems have promising properties conducive for radiation-resistant performance, they suffer beyond the design-limit from one or more damage processes such as void swelling, radiation embrittlement, phase instability, corrosion, and limited creep life.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Dynamic mode decomposition with core sketch

With the increase in collected data volumes, either from experimental measurements or high fidelity simulations, there is an ever-growing need to develop computationally efficient tools to process, analyze, and interpret these datasets. Modal analysis techniques have gained great interest due to their ability to identify patterns in the data and extract valuable information about the system being considered. Dynamic mode decomposition (DMD) relies on elements of the Koopman approximation theory to compute a set of modes, each associated with a fixed oscillation frequency and a decay/growth rate. Extracting these details from large datasets can be computationally expensive due to the need to implement singular value decomposition of the input data matrix. Sketching algorithms have become popular in numerical linear algebra where statistical theoretic approaches are utilized to reduce the cost of major operations. A sketch of a matrix is another matrix, which is significantly smaller, but still sufficiently approximates the original system. We put forth an efficient DMD framework, SketchyDMD, based on a core sketching algorithm that captures information about the range and corange (their mutual relationship) of input data. The proposed sketching-based framework can accelerate various portions of the DMD routines, compared to classical methods that operate directly on the raw input data. We conduct numerical experiments using the spherical shallow water equations as a prototypical model in the context of geophysical flows. In conclusion, we show that the proposed SketchyDMD is superior to existing randomized DMD methods that are based on capturing only the range of the input data.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Nondestructive flash cathode recycling

Effective recycling of end-of-life Li-ion batteries (LIBs) is essential due to continuous accumulation of battery waste and gradual depletion of battery metal resources. The present closed-loop solutions include destructive conversion to metal compounds, by destroying the entire three-dimensional morphology of the cathode through continuous thermal treatment or harsh wet extraction methods, and direct regeneration by lithium replenishment. Here, we report a solvent- and water-free flash Joule heating (FJH) method combined with magnetic separation to restore fresh cathodes from waste cathodes, followed by solid-state relithiation. The entire process is called flash recycling. This FJH method exhibits the merits of milliseconds of duration and high battery metal recovery yields of ~98%. After FJH, the cathodes reveal intact core structures with hierarchical features, implying the feasibility of their reconstituting into new cathodes. Relithiated cathodes are further used in LIBs, and show good electrochemical performance, comparable to new commercial counterparts. Life-cycle-analysis highlights that flash recycling has higher environmental and economic benefits over traditional destructive recycling processes.

25 ENERGY STORAGE↗

Manufacturing Processes for Permanent Magnets: Part I—Sintering and Casting

Abstract Permanent magnets (PMs) produce magnetic fields and maintain the field even in the presence of an opposing magnetic field. Electrical machines using permanent magnets are more efficient than those without. Currently, all known strong magnets contain rare earth (RE) elements, and they are core components of a wide range of applications including electric vehicles and wind turbines. RE elements such as Nd and Dy have become critical materials due to the growing demand and constrained supply. Improving the manufacturing process is effective in mitigating the RE criticality issue by reducing waste and improving parts consistency. In this article, the state of the industry for PM is reviewed in detail considering both the technical and economic drivers. The importance of RE elements is discussed along with their economic importance to green energy. The conventional sintering and casting manufacturing processes for commercial magnets, including Nd-Fe-B, Sm-Co, Alnico, and ferrite, are described in detail.

36 MATERIALS SCIENCE↗

Theoretical Correlation of Elemental Distribution of Nd and Pr in Ce-Fe-B Microstructure With Hard Magnetic Properties

Relatively resource-rich but property inferior-Ce-Fe-B magnet can be improved by partial replacement of Ce by Nd and/or Pr. In addition to the amount of Nd/Pr, their distribution profile in microstructure plays an important role. From our first principles density functional theory (DFT) calculation, the substitution energy of Ce by Pr/Nd is negative in Ce 2 Fe 14 B (2:14:1) while that for laves phase, CeFe 2 is positive, implying that Nd/Pr stabilize 2:14:1 and suppress the formation of the CeFe 2 phase. Further, micromagnetic simulation indicates that homogenized distribution of Nd/Pr improves squareness of demagnetization curve, while core (Ce-rich)-shell (Nd/Pr-rich) 2:14:1 grain structure enhances coercivity. Magnetic properties of Ce-Fe-B can be optimized by manipulating distribution profile of chemical element in microstructure based on their subtle difference in thermodynamic property, which is an effective pathway to design optimized chemical composition and processing route for high-performance magnet.

36 MATERIALS SCIENCE↗

Assessing mean climate change signals in the global CORDEX-CORE ensemble

The new Coordinated Output for Regional Evaluations (CORDEX-CORE) ensemble provides high-resolution, consistent regional climate change projections for the major inhabited areas of the world. It serves as a solid scientific basis for further research related to vulnerability, impact, adaptation and climate services in addition to existing CORDEX simulations. The aim of this study is to investigate and document the climate change information provided by the CORDEX-CORE simulation ensemble, as a part of the World Climate Research Programme (WCRP) CORDEX community. An overview of the annual and monthly mean climate change information in selected regions in different CORDEX domains is presented for temperature and precipitation, providing the foundation for detailed follow-up studies and applications. Initially, two regional climate models (RCMs), REMO and RegCM were used to downscale global climate model output. The driving simulations by AR5 global climate models (AR5-GCMs) were selected to cover the spread of high, medium, and low equilibrium climate sensitivity at a global scale. The CORDEX-CORE ensemble has doubled the spatial resolution compared to the previously existing CORDEX simulations in most of the regions (25 $\,\mathrm {km}$ (0.22 $^{\circ }$ /jats:inline-formula>) versus 50 $\,\mathrm {km}$ (0.44 $^{\circ }$ )) leading to a potentially improved representation of, e.g., physical processes in the RCMs. The analysis focuses on changes in the IPCC physical climate reference regions. The results show a general reasonable representation of the spread of the temperature and precipitation climate change signals of the AR5-GCMs by the CORDEX-CORE simulations in the investigated regions in all CORDEX domains by mostly covering the AR5 interquartile range of climate change signals. The simulated CORDEX-CORE monthly climate change signals mostly follow the AR5-GCMs, although for specific regions they show a different change in the course of the year compared to the AR5-GCMs, especially for RCP8.5, which needs to be investigated further in region specific process studies.

54 ENVIRONMENTAL SCIENCES↗

Skin factor and potential formation damage from chemical and mechanical processes in a naturally fractured carbonate aquifer with implications to CO 2 sequestration

Here, in this study, we investigate formation damage due to acidization and water injection tests into the naturally fractured carbonate Middle Duperow Formation at Kevin Dome, Montana, potentially diminishing the chance of a future successful Geological Carbon Sequestration (GCS) project. Multiple well-test analytical models, correlated with core description and lithology data, are used to determine flow behavior and communication between the water injection interval and surrounding formations. An improved three-dimensional (3D) geologic model with dual-continuum matrix and fracture properties is constructed based on most recent seismic, core, and water sample measurements. Brine injection is simulated to verify the interpretation from the analytical models, followed by CO 2 injection simulation. Geochemical calculations are performed to understand the in-situ processes that led to formation damage. Our findings suggest: (1) there are two possible scenarios that could lead to a positive total effective skin factor and permeability decline: partial penetration and formation damage; (2) analytical models indicate a positive total skin factor, contradicting results of a previous study suggesting that the well was mildly stimulated; (3) numerical simulation supports the formation damage hypothesis by matching the pressure buildup observed during the latter two brine injection tests; (4) several mechanical and chemical processes may have occurred during injection to clog the matrix/fracture system: anhydrite fines migration and/or calcite precipitation. We then make preventative suggestions for future GCS projects into carbonate reservoirs and remediation recommendations for GCS operation at the Kevin Dome.

54 ENVIRONMENTAL SCIENCES↗

Accuracy Enhancement of Nuclear Power Plant Simulators Utilizing High Accuracy Simulation Predictions

More recently, reactor core simulators for core designs associated with commercial nuclear power plants that utilize what is believed to be higher fidelity models have been developed. Features such as neutronics models that utilize transport equation solvers with fine spatial meshes and many energy-groups, thermal-hydraulic models that utilize sub-channel solvers with fine spatial mesh and capable of treating a wide range of fluid conditions, and fuel-coolant chemistry interaction models capable of treating CRUD deposition are to be found in these higher fidelity core simulators. These reactor core simulators require access to higher performance computers, characterized by many processors, cores and large memory. So associated with utilization of these simulators is access to high performance computers and ability to accommodate in one’s workflow longer execution times. By contrast, currently used core simulators by the nuclear industry can execute on engineering workstations and have execution times of seconds to minutes. The desirability for having short execution times is not only desired for support of time critical tasks but supports the mental process of decision making by engineers. The goal of the work reported upon here has the objective of retaining the fidelity of higher fidelity models while retaining the ability to utilize engineering workstations. Beyond the core simulator goal, additional goals of this work include incorporating the just described core simulator capability into a Nuclear Steam Supply System (NSSS) simulator, and to incorporate the resulting capability into an environment supportive of design and operational decision making associated with nuclear power stations. The model selected for the core neutronics model is the NESTLE code, for the core thermal-hydraulic model is the CTF code utilizing coarse mesh, and for the NSSS model is the RELAP5-3D code. WSC’s proprietary 3KEYMASTERTM platform is being used to provide software coupling, user interface, visualization, and reporting. The NESTLE core neutronics simulator was first integrated with the CTF core thermal-hydraulic simulator using CTF developed communication commands which are also used for CTF to communicate with RELAP5-3D under WSC’s proprietary 3KEYMASTERTM platform. To assure NESTLE prediction consistency with higher fidelity core neutronic simulators, buffer codes have been created to automatically generate from output files written by the VERA core simulator the NESTLE nodal neutronic parameter’ library, geometry, and pin-power reconstruction input files, thereby avoiding a number of challenges associated with utilizing lattice physics codes and providing consistency with VERA predictions. To treat absorber rod effects a multi-set library is utilized, where a set refers to a specific absorber rod fully inserted pattern. A coarse spatial mesh CTF model was developed with features added that support using CTF as envisioned in the engineering quality simulator. A hybrid meshing approach was implemented to allow for automated construction of models with mixed levels of refinement. Specifically, a core model could resolve some assemblies at a nodal level (4 subchannels per assembly) and others at a pin-resolution (one subchannel per coolant subchannel in the assembly). The intention is that this will allow for better resolution of limiting conditions such as DNBR and PCT, which are based on local rod and subchannel conditions. Further development was done of features that enhance the capabilities for the envisioned engineering quality simulator that has been developed, but now for RELAP-3D. The RELAP5-3D code development includes ability to model more than 999 components and the addition of the cross-channels turbulence mixing model and the void drift model that are implemented in CTF, aiming to achieve closer prediction agreement of the two codes for transient simulations, specifically, more accurate matches of the overall mass, momentum, and energy exchanges of both the liquid and gas phases between the neighboring core assemblies. Graphics were also developed for the Instructor Station for this project under WSC’s proprietary 3KEYMASTERTM platform to facilitate design and operational decision making.

42 ENGINEERING↗

Determination of the spent fuel decay heat with the VERA core simulator

VERA core simulator capabilities to predict spent fuel decay heat have been explored. The comparison with the Serpent2 and NEWT/TRITON sequence from the SCALE package, performed on the NPP Krško fuel test cases, has enabled independent verification of the successful implementation of the VERA depletion/decay calculation sequence applied on the extended nuclide set. Since the VERA is a 3-D core simulator, the focus in the rest of the paper was on the investigation of the 3-D effects and non-linearity of the soluble boron concentration averaging process, which are difficult to assess with most of available computational tools. A difference in the decay heat prediction between the 3-D and 2-D model approaches was analyzed. In addition, the impact of the Inconel grids on the decay heat was determined. Averaging the concentration of soluble boron over the fuel irradiation period has been found to be a viable approach, since it results in slight decay heat overprediction, which is considered conservative for most applications. Finally, demonstration on the Watts Bar Unit 1 cycle 1 depletion has shown formidable VERA capabilities to accurately predict spent fuel decay heat.

Kromar, Marjan↗

Nitride-Oxide-Metal Heterostructure with Self-Assembled Core–Shell Nanopillar Arrays: Effect of Ordering on Magneto-Optical Properties

Magneto-optical (MO) coupling incorporates photon-induced change of magnetic polarization that can be adopted in ultrafast switching, optical isolators, mode convertors, and optical data storage components for advanced optical integrated circuits. However, integrating plasmonic, magnetic, and dielectric properties in one single material system poses challenges since one natural material can hardly possess all these functionalities. Here, co-deposition of a three-phase heterostructure composed of a durable conductive nitride matrix with embedded core–shell vertically aligned nanopillars, is demonstrated. Additionally, the unique coupling between ferromagnetic NiO core and atomically sharp plasmonic Au shell enables strong MO activity out-of-plane at room temperature. Further, a template growth process is applied, which significantly enhances the ordering of the nanopillar array. The ordered nanostructure offers two schemes of spin polarization which result in stronger antisymmetry of Kerr rotation. The presented complex hybrid metamaterial platform with strong magnetic and optical anisotropies is promising for tunable and modulated all-optical-based nanodevices.

36 MATERIALS SCIENCE↗

Neutronic Consideration of TREAT Facility Fuel SiC Recladding

The Transient Reactor Test (TREAT) Facility is an air-cooled reactor composed of graphite-urania fuel encapsulated in zirconium alloy canisters and surrounded by ~2 ft (~61 cm) of nuclear grade graphite. The primary role of TREAT is to provide in-pile nuclear-heated safety research via transient testing [1]. Benchmark efforts have demonstrated sensitivity of TREAT neutronics models to graphite cross section data and key neutron poisons found in the fuel assemblies [2]. During fabrication of TREAT fuel assemblies, a small concentration of boron was inadvertently introduced with variable concentration into the aggregate of fuel blocks prepared for TREAT use. The concentration of boron, and its respective uncertainty, represent the most sensitive component in a neutronics study; unfortunately, nothing can be done to reduce or otherwise mitigate its impact. Hydrogen in the fuel blocks reduces the mean free path of the core and its true quantity and uncertainty is approximated. The hydrogen remains from pitch binder used in the fuel fabrication process and was not completely released due to incomplete fuel graphitization. Destructive fuel testing is necessary to quantify the actual hydrogen content and to improve benchmark model quality. A third neutron poison of some significance is the hafnium impurity in the Zircaloy-3 (Zry-3) assembly cladding. The quantity of hafnium is expected to be within nominal manufacturing limits for nuclear grade zircaloy. Recladding the fuel assemblies with material that is less neutron absorbing is expected to benefit reactor neutron economy. Moreover, TREAT’s total transient energy is restricted based on the rate of Zry-3 oxidation in TREAT’s air coolant environment. Hence, cladding with more benign air reaction kinetics could dramatically uprate the facility’s experimental capability. Silicon carbide (SiC) has been proposed as a candidate material for recladding TREAT assemblies, as SiC/SiC demonstrate favorable properties within nuclear environments [3]. The current operational limits of TREAT are restricted by the oxidation of Zry-3. Change of the cladding to SiC could feasibly double the current temperature limitation. Recladding opportunities allow for previously damaged fuel assemblies to be returned to service, as Zry-3 is not commercially available. The initial effort required to consider proceeding with any recladding effort is to neutronically characterize key reactor parameters while replacing Zry-3 with SiC. A characterization summary, with respective results, is provided herein.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Water isotopes, climate variability, and the hydrological cycle: recent advances and new frontiers

Abstract The hydrologic cycle is a fundamental component of the climate system with critical societal and ecological relevance. Yet gaps persist in our understanding of water fluxes and their response to increased greenhouse gas forcing. The stable isotope ratios of oxygen and hydrogen in water provide a unique opportunity to evaluate hydrological processes and investigate their role in the variability of the climate system and its sensitivity to change. Water isotopes also form the basis of many paleoclimate proxies in a variety of archives, including ice cores, lake and marine sediments, corals, and speleothems. These records hold most of the available information about past hydrologic variability prior to instrumental observations. Water isotopes thus provide a ‘common currency’ that links paleoclimate archives to modern observations, allowing us to evaluate hydrologic processes and their effects on climate variability on a wide range of time and length scales. Building on previous literature summarizing advancements in water isotopic measurements and modeling and describe water isotopic applications for understanding hydrological processes, this topical review reflects on new insights about climate variability from isotopic studies. We highlight new work and opportunities to enhance our understanding and predictive skill and offer a set of recommendations to advance observational and model-based tools for climate research. Finally, we highlight opportunities to better constrain climate sensitivity and identify anthropogenically-driven hydrologic changes within the inherently noisy background of natural climate variability.

Dee, Sylvia (ORCID:000000022140785X)↗

π-Extension and chlorination of non-fullerene acceptors enable more readily processable and sustainable high-performance organic solar cells

Organic solar cells (OSCs) processed without halogenated solvents and complex treatments are essential for future commercialization. Herein, we report three novel small molecule acceptors (NFAs) consisting of a Y6-like core but with π-extended naphthalene with progressively more chlorinated end-capping groups and a longer branched chain on the Nitrogen atom. These NFAs exhibit good solubilities in non-chlorinated organic solvents, broad optical absorptions, close π-π stacking distances (3.63–3.84 Å), and high electron mobilities (~10 -3 cm 2 V -1 s -1 ). Further, the o-xylene processed and as-cast binary devices using PM6 as the donor polymer exhibit a PCE increasing upon progressive chlorination of the naphthalene end-capping group from 8.93% for YN to 14.38% for YN-Cl to 15.00% for YN-2Cl. Furthermore similarly processed ternary OSCs were fabricated by employing YN-Cl and YN-2Cl as the third component of PM6:CH1007 blends (PCE = 15.75%). Compared to all binary devices, the ternary PM6:CH1007:YN-Cl (1:1:0.2) and PM6:CH1007:YN-2Cl (1:1:0.2) cells exhibit significantly improved PCEs of 16.49% and 15.88%, respectively, which are among the highest values reported to date for non-halogenated solvent processed OSCs without using any additives and blend post-deposition treatments.

14 SOLAR ENERGY↗

Production Facility Simulations for Annular LEU Targets

Eden Radioisotopes, LLC is designing a new molybdenum-99 (Mo-99) production facility based on a TRIGA-sized reactor with a core composed of low enriched uranium (LEU) targets. Reactor production is designed to exceed U.S. demand for Mo-99 using the fission processes. The nominal operational power is 1.8MW (less than 2.0MW, to satisfy the “non-power” reactor requirement) and desired irradiation scenarios include 7, 14, or 21 days of the irradiation for each target element. Safety limits for reactor operating margins are associated with such physical phenomena as fission gas release, fuel swelling, and stress cracking. As shown in the literature, one of the critical parameters defining safety margins for metallic uranium fuel is swelling. In its turn the fuel operational temperature is the main parameter impacting the swelling rate. This report documents the results of consecutive studies of reactor criticality, fission energy depositions, and cooling conditions for the target. The maximum temperature calculated for the LEU targets allows us to choose appropriate modeling approximation of the swelling. All obtained results refer to the preliminary targets and core designs provided by Eden. A criticality analysis was performed, and the results are listed mainly to cross-check Eden’s safety report and assume maximal neutron field disturbance for maximal reactivity. A brief description of the metallic uranium swelling model is provided in the Appendix.

07 ISOTOPE AND RADIATION SOURCES↗

Redox-active dinuclear oxorhenium(V) pyrazolate complexes

Four new structurally similar dinuclear oxorhenium(V) complexes, [{Re(O)X(PPh 3 )} 2 (μ-O)(μ-4-x'-pz) 2 ], where pz = pyrazolate anion, X = X' = Cl (1) and Br (4), X = Cl, X' = Br (2), and X = Br, X' = Cl (3), have been synthesized and characterized. Little variation in spectroscopic features – 1 H NMR, IR, UV–Vis – exists among the four complexes. All complexes possess a bent Re-O-Re core as well as distorted octahedral coordination geometry around the rhenium centers. Finally, a reversible one-electron electrochemical process is observed at approximately 0.84 V vs. Fc + /Fc in all four complexes; however, changing the terminal halide from chloride to bromide slightly destabilizes the oxidized Re(VI) center.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Potent strategy towards strongly emissive nitroaromatics through a weakly electron-deficient core

Nitroaromatics seldom fluoresce. The importance of electron-deficient (n-type) conjugates, however, has inspired a number of strategies for suppressing the emission-quenching effects of the strongly electron-withdrawing nitro group. Here, we demonstrate how such strategies yield fluorescent nitroaryl derivatives of dipyrrolonaphthyridinedione (DPND). Nitro groups near the DPND core quench its fluorescence. Conversely, nitro groups placed farther from the core allow some of the highest fluorescence quantum yields ever recorded for nitroaromatics. This strategy of preventing the known processes that compete with photoemission, however, leads to the emergence of unprecedented alternative mechanisms for fluorescence quenching, involving transitions to dark nπ* singlet states and aborted photochemistry. Forming nπ* triplet states from ππ* singlets is a classical pathway for fluorescence quenching. In nitro-DPNDs, however, these ππ* and nπ* excited states are both singlets, and they are common for nitroaryl conjugates. Understanding the excited-state dynamics of such nitroaromatics is crucial for designing strongly fluorescent electron-deficient conjugates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗