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At least 631 records · Page 35

Observation of Persistent Zero Modes and Superconducting Vortex Doublets in UTe 2

Superconducting vortices can reveal electron pairing details and nucleate topologically protected states. Yet, vortices of bulk spin-triplet superconductors have never been visualized at the atomic scale. Recently, UTe 2 has emerged as a prime spin-triplet superconductor, but its superconducting order parameter is elusive, and whether time-reversal symmetry (TRS) is broken remains unsettled. Here, in this work, we visualize vortices on the (011) surface of ultraclean UTe 2 single crystals (T c = 2.1 K) using scanning tunneling microscopy (STM). We introduce $\frac{d^{2}𝐼}{d𝑉^{2}}$ imaging as an effective technique for vortex visualization in superconductors with substantial residual zero-energy density of states (DOS), as in UTe 2 . Anisotropic single-flux-quantum vortices, with coherence lengths of ∼12 nm (4 nm) parallel (perpendicular) to the a -axis, form a triangular vortex lattice (VL) under a small out-of-plane magnetic field. The invariance of vortex structures and VL under changes of field polarity and cooling history strongly supports time-reversal invariant superconductivity under zero field. At vortex cores (VCs), nonsplit, spectrally sharp zero-bias conductance peaks (ZBPs) persist up 8 T that are consistent with symmetry-protected Majorana zero modes (MZMs) in a topological vortex line. Close examination of vortex structures reveals a mirror-asymmetric doublet─one with ZBPs and another with an enhanced apparent gap, possibly originating from a field-induced multicomponent order parameter.

UTe2↗

Mechanism of Mesoscale Woodpile Development via Photoelectrochemical Deposition of Se–Te

A combination of experiments and optical modeling provided insight into the mechanism of mesoscale woodpile formation in response to an orthogonal shift in polarization during photoelectrochemical deposition of Se–Te. Cathodic deposition of semiconducting Se–Te using spatially uniform, linearly polarized illumination produced arrays of lamellae that were aligned parallel to the optical E-field oscillation. Continued deposition in conjunction with an orthogonal shift in the polarization direction then produced aligned bridging features that spanned the void space between, and were orthogonal to, the preexisting lamellae. The height and pitch, respectively, in each layer of the woodpile were a function of the charge density and illumination wavelength during deposition. A Monte Carlo model, in which material addition was scaled by the absorption magnitude obtained from electromagnetic simulations, produced morphologies that were nominally identical to those observed experimentally. Here, the formation of mesoscale woodpiles is consistent with a mechanism that involves a series of spontaneously initiated, concerted light–matter interactions during the photoelectrochemical deposition process.

absorption↗

Dynamic Behavior of Bound Interlayer Excitons in Interlayer-Doped Cs 3 Bi 2 Br 9 Vacancy-Ordered Perovskite

Interlayer doping of the vacancy-ordered 2D perovskite Cs 3 Bi 2 Br 9 (CBB) enables the formation of bound interlayer excitons (BIEs), a unique charge-transfer excited state within the layered solid. BIEs previously reported with silver (Ag + ) as an interlayer dopant exhibited bright broadband photoluminescence (PL) with prolonged lifetime at room temperature, offering potential applications in efficient white light emission, photocatalysis, and optoelectronics. However, the dynamic behavior of radiation and excited carriers remains poorly understood due to the limitations of ensemble spectroscopic measurements. Here, we investigate the temperature-dependent dynamics of Ag-doped Cs 3 Bi 2 Br 9 (Ag-CBB) using single-particle time-resolved PL spectroscopy and ultrafast transient absorption imaging. Single-particle PL measurements reveal three distinct emission regimes across temperature: (i) BIE-dominant emission at high temperatures, (ii) a mixture of radiation from BIEs and self-trapped excitons (STEs) at intermediate temperatures, and (iii) STE-dominant emission below 100 K. Rapid transient absorption mapping using Parallel Rapid Imaging with Spectroscopic Mapping (PRISM) reveals subpicosecond STE formation in pristine CBB and long-lived photoinduced absorption by BIEs, consistent with electron–hole separation and suppressed STE transfer. The spatial uniformity of these signals confirms homogeneous Ag doping across single crystals. These findings highlight the role of Ag interlayer dopants in governing the BIE dynamics.

bound interlayer exciton↗

3D Printing ofThermally Responsive Shape Memory LiquidCrystalline Epoxy Networks

Abstract A two-component liquid crystalline epoxy network (LCEN) with shape memory behavior was developed and evaluated as a candidate material for 3D printing. The cure kinetics of the uncured material and the shape memory properties of the cured LCEN were investigated by using parallel plate rheology and dynamic mechanical analysis, respectively. A commercially available fumed silica additive was introduced to the neat, uncured material to improve the rheological properties for 3D printing. The addition of fumed silica was found to increase the yield stress, shear-thinning behavior, and toughness of the uncured epoxy ink. Polarized light microscopy, differential scanning calorimetry, and wide-angle X-ray scattering measurements between the neat and additive-modified LCEN suggested a reduction in liquid crystalline alignment in the modified LCEN, owing to interactions between crystalline domains and fumed silica, which in turn influenced the mechanical behavior. Overall, the additive was found to be successful in preserving the shape memory properties of LCEN while improving its printability.

Chemistry↗

Rapid Evaluation of Amine-Functionalized Solvents for Biomass Deconstruction Using High-Throughput Screening and One-Pot Enzymatic Saccharification

Efficient and sustainable pretreatment of lignocellulosic biomass is critical for biofuel and biochemical production, yet its optimization is often hindered by slow, labor-intensive experimental methods. Here, we report the first demonstration of a custom-built, miniaturized, high-throughput screening platform integrated with one-pot enzymatic saccharification, enabling parallel evaluation of solvent type, feedstock, and temperature with minimal material use and high reproducibility. As a proof-of-concept, the HTX platform was used to screen five amine-functionalized solvents, including isopropanolamine, butylamine, N-methylbutylamine, ethanolamine, and ethanolamine acetate across three bioenergy crops (sorghum, poplar, and switchgrass) and pretreatment temperatures ranging from 80 to 140 °C. Vacuum drying successfully removed more than 99% of the solvents from the pretreated biomass, eliminating the need for water washing prior to saccharification. Isopropanolamine and N-methylbutylamine yielded the highest glucose (70–80%) and xylose (58–67%) release, with trends reflecting feedstock recalcitrance. The produced hydrolysates supported robust growth of an engineered strain of the yeast Rhodosporidium toruloides, confirming biocompatibility. This high-throughput platform provides a scalable, feedstock-agnostic framework for rapid pretreatment screening, accelerating solvent–feedstock pairing and process optimization. Its ability to integrate pretreatment, solvent removal, saccharification, and microbial conversion in a miniaturized format offers significant advantages for cost-competitive biorefinery development.

Biomass↗

Optimizing Desalination Operations for Energy Flexibility

Despite the value of energy optimization in desalination processes, modeling dynamic operations for monthly billing periods has remained a computational challenge. This work proposes a framework for energy flexibility optimization, which includes new modeling features for independent operation of parallel skids, start-up delays associated with chemical stabilization, the consideration of industrial energy tariff structures, and inclusion of hourly electrical carbon intensities. This is done using a modular and computationally efficient formulation that guarantees a globally optimal solution with standard optimization solvers. In this study, the approach is demonstrated in two distinct case studies: a seawater desalination plant in Santa Barbara, CA, and an indirect potable reuse facility in San Jose, CA. Trends predicted from the model are validated against operational facility measurements from a demand response shutdown event. Preliminary results show that optimizing energy flexibility can result in 18.51% monthly cost savings over energy efficiency-optimized operation. The value extracted from a facility-wide shutdown during peak electricity price hours is hampered by start-up delays in post-treatment chemical stabilization. In cases in which a facility does not have much excess capacity, using a flow equalization tank or operating over a wide recovery range may be cost-effective.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Engineering and Application of a Thermostable MHETase for PET Depolymerization

Enzymatic hydrolysis of poly(ethylene terephthalate) (PET) releases mono(2-hydroxyethyl) terephthalate (MHET) as a major product, the accumulation of which can prolong reactor residence times and complicate downstream monomer separations. The use of a MHETase enzyme can enable MHET hydrolysis to the monomers, terephthalic acid and ethylene glycol, but industrial PETases typically operate at thermophilic temperatures and the well-known MHETase from Ideonella sakaiensis is a mesophilic enzyme, thus warranting the development of thermophilic MHETases. Here, we characterize thermostable MHET-active enzymes from a natural diversity screen by applying a hidden Markov model based on the previously reported, archaeal ferulic acid esterase, PET46. We identified enzymes with higher thermostability than PET46 and quantified their MHETase activity in reactions at 70 °C. The crystal structure of MHT077, the homologue with the highest MHETase activity and an apparent melting temperature (T m,app ) of 94.6 °C, informed site saturation mutagenesis in the active site and lid-domain interface. MHT077 exhibited a ∼100-fold slower unfolding rate at 65 °C than PET46, indicating substantially greater kinetic stability. In parallel, we applied evolution-informed design, a probabilistic model that leverages coevolutionary patterns in large multiple sequence alignments, to improve the activity and thermostability of five ferulic acid esterases. One design, EV-MHT043–5 was identified with a comparable thermostability (T m,app = 96.1 °C) and a 3-fold improvement in its MHETase activity relative to the wildtype enzyme, MHT043. Combination variants of beneficial mutations were screened and afforded a variant, MHT077 LFK , which reduced MHET accumulation in bioreactor experiments with postconsumer PET waste. Overall, this study expands the known MHET-hydrolyzing protein scaffolds available for enzymatic PET recycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vision and Development of a Design, Implementation, and Verification Automation (DIVA) Software Platform for DNA Construction

Abstract DNA construction, while a prerequisite to many biological endeavors, is often a time-consuming distraction from an individual’s primary research objectives. We envisioned that with the right software infrastructure and cultural mindset, a single person could execute in parallel the batched DNA construction tasks of an entire research institute, at scales realizing efficiency gains through process and laboratory automation. In pursuit of this vision, we developed the Design, Implementation, and Verification Automation (DIVA) software platform. DIVA’s web interface enables researchers to design DNA constructs (using visual biological computer-aided design tools and biological parts repositories), submit designs for construction to dedicated staff, and track DNA construction as it progresses. DIVA supports the dedicated staff through the DNA construction process and records both successful and unsuccessful attempts toward improving the overall process. The platform is publicly available at public-diva.jbei.org and its open-source code through github.com/JBEI/DIVA.

Plahar, Hector [DOE Agile BioFoundry , , ,; DOE Jo↗

Ethylene Polymerizations Catalyzed by Fluorinated “Sandwich” Diimine-Nickel and Palladium Complexes

Nickel and palladium complexes bearing “sandwich” diimine ligands with perfluorinated aryl caps have been synthesized, characterized, and explored in ethylene polymerization reactions. The X-ray crystallographic analysis of the precatalysts 16 and 6b show differences from their non-fluorinated analogues 17 and 19, with the perfluorinated aryl caps centered precisely over the nickel and palladium centers which results in higher buried volumes of the metal centers relative to the non-fluorinated analogs. The sandwich diimine palladium complexes 5a and 5b containing perfluorinated aryl caps polymerize ethylene in a controlled fashion with activities that are substantially increased compared with their non-fluorinated analogues. Migratory insertion rates in relevant methyl ethylene complexes agree with activities exhibited in bulk polymerization experiments. DFT studies suggest that facility of ethylene rotation from its preferred orientation perpendicular to the Pd-alkyl bond into a parallel in-plane conformation contributes to the higher polymerization activity for 5b relative to 18a. For these palladium systems polymer molecular weights can be controlled via hydrogen addition (hydrogenolysis) which is unusual for late transition metal-catalyzed olefin polymerizations with no catalyst deactivation occurring. Sandwich diimine nickel complexes 6a and 6b with perfluorinated aryl caps show ethylene polymerization activities that are about half that of classical tetraisopropyl-substituted catalyst 2 but again are more active than the analogous nonfluorinated sandwich complexes. Ethylene polymerizations exhibit living behavior and branched ultra-high molecular weight polyethylenes (UHMWPEs) with very low molecular weight distributions (less than 1.1) are obtained. The activated nickel catalysts are stable in the absence of monomer and show good long-term stability at 25 °C.

36 MATERIALS SCIENCE↗

Short-Wave Infrared Upconverting Nanoparticles

Optical technologies enable real-time, noninvasive analysis of complex systems but are limited to discrete regions of the optical spectrum. While wavelengths in the short-wave infrared (SWIR) window (typically, 1700-3000 nm) should enable deep subsurface penetration and reduced photodamage, there are few luminescent probes that can be excited in this region. Here, we report the discovery of lanthanide-based upconverting nanoparticles (UCNPs) that efficiently convert 1740 or 1950 nm excitation to wavelengths compatible with conventional silicon detectors. Screening of Ln3+ ion combinations by differential rate equation modeling identifies Ho3+/Tm3+ or Tm3+ dopants with strong visible or NIR-I emission following SWIR excitation. Experimental upconverted photoluminescence excitation (U-PLE) spectra find that 10% Tm3+-doped NaYF4 core/shell UCNPs have the strongest 800 nm emission from SWIR wavelengths, while UCNPs with an added 2% or 10% Ho3+ show the strongest red emission when excited at 1740 or 1950 nm. Mechanistic modeling shows that addition of a low percentage of Ho3+ to Tm3+-doped UCNPs shifts their emission from 800 to 652 nm by acting as a hub of efficient SWIR energy acceptance and redistribution up to visible emission manifolds. Parallel experimental and computational analysis shows rate equation models are able to predict compositions for specific wavelengths of both excitation and emission. These SWIR-responsive probes open a new IR bioimaging window, and are responsive at wavelengths important for vision technologies.

Qi, Xiao↗

Autonomous Nanoparticle Synthesis Guided by In Situ Multiscale Structural Characterization

Autonomous synthesis platforms promise rapid exploration of vast parameter spaces; yet, integrating in situ structural characterization in closed-loop synthesis optimization remains challenging. We demonstrate a realization of such a closed-loop platform coupled with a droplet-flow microreactor, in situ X-ray scattering methods (SAXS/WAXS), and Gaussian process optimization to synthesize citrate-reduced Au nanoparticles with targeted characteristics. The system efficiently explored ∼19,000 synthesis recipes through 365 experiments, achieving precise control over size (4–60 nm) and polydispersity (σ < 0.11) across large citrate/gold ratios, exceeding traditional synthesis boundaries (1–10). Beyond confirming classical Turkevich–Frens trends, partial-dependence analysis revealed strong nonlinear coupling among precursor, citrate, and pH effects. Combining quantitative SAXS/WAXS analysis with electron microscopy characterization, we uncovered that crystallite size (d c ) and particle size (d) follow d c = 0.18d + β, where synthesis chemistry controls the intercept β while maintaining a universal slope. This parallel-band structure enables independent tuning of crystallite domain size at fixed particle diameter through a combination of chloride, gold precursor, citrate, and pH contributions (cross-validated Spearman ρ = 0.7 ± 0.1). High-resolution electron microscopy shows multiple lattice-fringe orientations within single particles, directly confirming polycrystalline domains and the ability to tune d c at the fixed d. The platform’s validation includes indistinguishable static versus flowing measurements, stable droplet transport at 100 °C, and <5% run-to-run variation, establishing a robust framework for mapping and controlling multiscale nanoparticle structure across expansive chemical spaces. In conclusion, the developed closed-loop platform can be applied to a borad range of nanosyntheis processes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Discovery and Synthesis of a Family of Boride Altermagnets

Borides are a rich material family. To push the boundaries of borides’ properties and applications into broader fields, we have conducted systematic theoretical and experimental searches for synthesizable phases in ternary borides TM 2 B 2 (T = 3d, M = 4d/5d transition metals). We find that TM 2 B 2 in the FeMo 2 B 2 -type and CoW 2 B 2 -type structures form a large family of stable/metastable materials of 120 members. Among them, we identify 40 materials with stable magnetic solutions. Further, we discover 11 altermagnets in the FeMo 2 B 2 -type structure. So far, boride altermagnets are rare. In these altermagnets, T = Fe or Mn atoms are arranged in parallel T-chains with strong ferromagnetic intrachain couplings and antiferromagnetic interchain couplings. They simultaneously exhibit electronic band spin splitting, typical of ferromagnetism, and zero net magnetization, typical of antiferromagnetism. They also exhibit magnonic band chiral splitting. Both effects originate from the unique altermagnetic symmetries crucially constrained by the nonmagnetic atoms in the structure. Transport properties of relevance to spintronic applications, including the strain-induced spin-splitter effect and anomalous Hall effect, are predicted. An iodine-assisted synthesis method for TM 2 B 2 is developed, using which 7 of the predicted low-energy phases are experimentally synthesized and characterized, including 4 altermagnets. This work expands the realm of borides by offering new opportunities for studying altermagnetism and altermagnons in borides. It also provides valuable insights into the discovery and design of altermagnets. Here, by demonstrating that altermagnets can exist as families sharing a common motif, this work paves a feasible route for discovering altermagnets by elemental substitutions and high-throughput computations.

Chemical structure↗

High-Throughput Discovery Illuminates Design Principles and Limits for Long-Lived Charged Species in Organic Electrolytes

The chemical stability of charged molecules in all-organic redox flow batteries (RFBs) is required for the prolonged operation of these devices. Molecular engineering and electrolyte optimization are used to mitigate parasitic reactions and extend the lifetimes of the charge carriers. However, how much can structural variation extend the lifetime? To probe this query, we designed a high-throughput kinetic study of the radical cation of N-methylphenothiazinium, guided by statistical sampling and learning algorithms. Using Argonne’s autonomous discovery facility, we conducted over 6,000 kinetic experiments with robotic sample preparation, parallel kinetic measurements, and machine learning inputs, testing 188 solvent molecules selected from a space of over 540 candidates from 11 chemical classes. Algorithmic selections guided us to stable solvent candidates, which were further tested in high concentration with and without supporting electrolyte. Our findings reveal the inherent difficulty of exceeding the current state of the art through solvent variation. The desired stability is statistically rare and poorly predictable. Among the many tested, only three solvents significantly outperformed our baseline, acetonitrile─and none by more than a factor of 3─suggesting a general challenge in achieving the necessary techno-economic targets. Furthermore, we suggest that self-discharge through solvent homolysis is the cause of the observed limitations. Several structural motifs contribute to >1,000 h half-life stability including molecular simplicity, symmetry, oxidation complement, and strategic fluorination. Importantly, this workflow establishes effective assays for diagnosing and predicting oxidative stress for highly stable liquid electrolytes in all batteries.

Batteries↗

Atomic-Scale Imaging Reveals Polar-π Interactions in Two-Dimensional Molecular Superlattices

Controlling coassembly of synthetic oligomers into binary superlattices at the atomic level is challenging. Here, we report a strategy for programming polar-π interactions in oligomeric peptoids, a class of sequence-defined peptidomimetics, facilitating the formation of homogeneous two-dimensional (2D) superlattices. N-2-phenylethyl and N-(2-perfluorophenyl)ethyl side chains, similar in size, but with contrasting electrostatic characteristics, were introduced at defined sequence positions to generate favorable dipolar aromatic interactions. The resulting nanosheets exhibit different crystal motifs depending on the side chain interactions: systems containing only one type of aromatic side chain form a parallel V-shaped motif driven by π-π interactions, whereas a combination of both types of aromatic side chains, either within one backbone or through the coassembly of two distinct peptoids, adopt an antiparallel V-shaped superlattice with higher thermal stability, driven by polar-π interactions. Cryogenic transmission electron microscopy directly resolved the packing arrangement of perfluorophenyl and phenyl rings in individual nanosheet superlattices, confirming that intermolecular polar-π interaction dominates the superlattice motifs and increases lattice stability. Molecular dynamics simulations and density functional theory calculations further substantiate the energetic favorability of polar-π interactions over π-π interactions, rationalizing the formation of homogeneous superlattices with enhanced thermal stability. Our discoveries establish a design principle for binary coassembly using sequence-defined oligomers, which enables control over unit cell geometry, lattice stability, and molecular registration through aromatic side chain polarization and sequence control. This ability to program atomic-scale binary superlattices opens new avenues for designing functional 2D soft materials.

Lee, Yen Jea [Lawrence Berkeley National Laborator↗

Multimodal Nanoscale Mapping of Local Structure and CO 2 Adsorption in Metal–Organic Frameworks

Diamine functionalization of the metal−organic framework Mg 2 (dobpdc) (dobpdc 4− = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) significantly enhances its selectivity for CO 2 capture from flue gases and air. The structure and CO 2 capacity of such materials are typically assessed using bulk techniques that rely on averaging signal over large ensembles of unit cells, obscuring local heterogeneities, such as variations in CO 2 occupancy across individual nanocrystals. To resolve this limitation, we demonstrate a multimodal, nanoscale characterization of Mg 2 (dobpdc) appended with 1,3-diaminopropane. By employing recently developed characterization techniques at progressively smaller length scales, we uncover insights from correspondingly smaller populations of unit cells. First, we use parallel-beam 3D electron diffraction (3D ED) to identify a prominent expansion in lattice parameters upon desorption of CO 2 , as observed at the level of single nanocrystals. Second, we use convergent-probe 4D scanning transmission electron microscopy (4D-STEM) to quantify associated differences in lattice strain as a function of gas loading and diamine appending. These measurements sample small subvolumes within individual nanocrystals. Finally, we apply infrared scattering scanning near-field optical microscopy (IR s- SNOM) to confirm variable CO 2 chemisorption across adsorption sites at the surface of single nanocrystals. This multimodal, multiscale approach allows us to map heterogeneity within individual nanocrystals. Collectively, these findings emphasize the importance of local, nanoscale characterization of metal−organic frameworks in revealing previously unresolvable features that impact their performance.

Karstens, Sarah L. [University of California, Berk↗

Native Architecture of Wheat Straw Cell Walls: A Unified Model from X-ray Scattering and Solid-State NMR

Plant secondary cell walls constitute the dominant reservoir of renewable biomass, comprising tightly packed cellulose, hemicellulose, and lignin at the nanoscale. Recent advances in solid-state NMR spectroscopy and the availability of small-angle X-ray scattering for biomass characterization have led to an accumulation of experimental data on cell wall organization, yet no explicit structure model has simultaneously satisfied both Xray and NMR observations. Using wheat straw as a model system, we propose a structural framework consistent with current knowledge of cellulose biosynthesis, X-ray scattering data, and one- and two-dimensional 13 C solid-state NMR spectra. In this model, 18-chain elementary fibrils align in parallel and populate the cross-section at random. Arabinose-substituted xylan shows no conformational dependence for cellulose-binding in wheat, and only a minor fraction of 2-fold xylan appears in close proximity to cellulose, unlike in Arabidopsis, where xylan is more tightly attached to the cellulose surface. While NMR data cannot unambiguously resolve the internal arrangement of the 18 glucan chains, X-ray scattering profiles uniquely constrain the fibril size and exclude the possibility of tight bundling in the intact walls. The specific interaction between the matrix polymers and the cellulose elementary fibrils must be reconsidered in light of the small interfibril spaces, which bring the matrix components into spatial proximity with cellulose even in the absence of attractive interactions. These findings provide fundamental molecular-level insight into cellulose fibril architecture and matrix−polymer interactions, resolving longstanding discrepancies between spectroscopic and scattering data and advancing our understanding of biopolymer assembly into structurally and functionally versatile lignocellulosic biomaterials.

Carbohydrates↗

Interfacial Inversion of Stealth Surfactants

Amphiphilic macromolecular surfactants segregate to liquid–liquid interfaces, thereby reducing the interfacial tension and free energy. Here, we investigated “stealth surfactants” in the form of core–shell bottlebrush polymers comprised of pH-responsive diblock copolymer side chains forming a hydrophilic core and a hydrophobic shell, enabling solubility in oil. At liquid–liquid interfaces, these polymers undergo a structural “inversion”, with hydrophilic blocks segregating into the aqueous phase and hydrophobic blocks residing in the oil phase. The reconfiguration kinetics and surfactant properties are influenced by multiple factors, including the molecular weights of the backbone and side chain components, the hydrophilic-to-hydrophobic balance of the side chains, and the pH of the aqueous phase. An observed nonmonotonic dependence of interfacial tension with time is attributed to a progressive structural inversion, where the projected area of the macromolecule onto the interface decreases. To validate this inversion hypothesis, interfacial properties were characterized by sum-frequency generation vibrational spectroscopy, which revealed configurational changes of the core–shell bottlebrush polymers at the fluid interface and revealed a pH-dependent interfacial coverage. Coarse-grained molecular dynamics simulations supported these experimental findings, showing that the pH-responsive core and hydrophobic shell assume a time-averaged configuration with orientations parallel and perpendicular to the plane of the interface, respectively. These findings open routes to design multistimuli-responsive polymeric surfactants and compatibilizers, expanding their potential applications in advanced interfacial systems.

Stealth surfactants↗

Pursuing Heteroleptic Ligand Design Principles for Photoactive Fe Complexes with Ultrafast X-ray Emission and Variable-Temperature Optical Spectroscopies

Understanding the key parameters that govern the photophysical and photochemical properties of transition metal complexes is essential for the development of efficient photosensitizers for photocatalytic applications. Achieving this objective necessitates clear and detailed investigations of their electronic excited states, for which time-resolved metal Kβ X-ray emission spectroscopy (XES) has proven highly effective. Here, we present a time-resolved Fe Kβ XES study of a heteroleptic Fe(II) polypyridyl carbene complex, [Fe(phen) 2 (C 4 H 10 N 4 )] 2+ (1; phen = 1,10-phenanthroline), utilizing both the valence-to-core and Kβ mainline spectral regions, complemented by variable-temperature transient optical absorption (VT-TA) spectroscopy. Detailed analysis of the time-resolved Kβ XES data, supported by density functional theory (DFT) calculations and an Eyring analysis of the VT-TA data, reveals parallel excited state relaxation dynamics that support an assignment of the long-lived excited state to a triplet metal-centered state. Placing these results in the context of prior studies of heteroleptic Fe(II) polypyridyl cyanide complexes motivated a series of DFT calculations to investigate the effects of ligand structural flexibility and arrangement. These calculations reinforce the experimentally derived conclusion that constraining structural flexibility with multidentate ligands significantly impacts the excited state relaxation dynamics. Furthermore, our study emphasizes that the arrangement of strong field ligands in heteroleptic complexes substantially affects the energy of Jahn–Teller active triplet metal-centered states in low-spin d 6 metal complexes. Together, these findings provide synthetic design principles for extending metal-to-ligand charge transfer excited state lifetimes of heteroleptic Fe complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗