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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Pressure-Induced Stacking of Rhodamine 6G Molecules

Extended conjugation of molecular π systems are of great significance for solar cells and organic light-emitting diodes as these can serve as new light absorbing and emitting chromophores. This research demonstrates the potential of using pressure and solvent environment to create larger assemblies of molecular π-conjugated systems. Here, we selected rhodamine 6G (Rh6G) to study the pressure-induced stacking of molecules in three different solvents: methanol (MeOH), isopropanol (IPA), and 16:3:1 mixture of methanol: ethanol: water (MEW). Absorption, emission, and fluorescence lifetime were studied at pressures up to 11.38 GPa. We found that pressure-induced stacking mechanisms can present solvent dependence: high pressures tend to create emissive Haggregates in MeOH and MEW, but excimers in IPA. This work guides and demonstrates routes to stacking of organic molecules using high pressures and provides fundamental insights into the formation of extended conjugation π systems.

Johnson, Kade [Univ. of Texas at San Antonio, TX (↗
DOE OSTI2021

Non-Adiabatic Excited State Molecular Dynamics Methodologies: comparison and convergence

Direct atomistic simulation of nonadiabatic molecular dynamics is a challenging goal that allows important insights into fundamental physical phenomena. A variety of frameworks, ranging from fully quantum treatment of nuclei to semiclassical and mixed quantum–classical approaches, were developed. These algorithms are then coupled to specific electronic structure techniques. Such diversity and lack of standardized implementation make it difficult to compare the performance of different methodologies when treating realistic systems. Here, we compare three popular methods for large chromophores: Ehrenfest, surface hopping, and multiconfigurational Ehrenfest with ab initio multiple cloning (MCE-AIMC). These approaches are implemented in the NEXMD software, which features a common computational chemistry model. The resulting comparisons reveal the method performance for population relaxation and coherent vibronic dynamics. Finally, we study the numerical convergence of MCE-AIMC algorithms by considering the number of trajectories, cloning thresholds, and Gaussian wavepacket width. Our results provide helpful reference data for selecting an optimal methodology for simulating excited-state molecular dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Nanoscale Confinement of Photo-Injected Electrons at Hybrid Interfaces

A prerequisite for advancing hybrid solar light harvesting systems is a comprehensive understanding of the spatiotemporal dynamics of photoinduced interfacial charge separation. Here, we demonstrate access to this transient charge redistribution for a model hybrid system of nanoporous zinc oxide (ZnO) and ruthenium bipyridyl chromophores. The site-selective probing of the molecular electron donor and semiconductor acceptor by time-resolved X-ray photoemission provides direct insight into the depth distribution of the photoinjected electrons and their interaction with the local band structure on a nanometer length scale. Our results show that these electrons remain localized within less than 6 nm from the interface, due to enhanced downward band bending by the photoinjected charge carriers. This spatial confinement suggests that light-induced charge generation and transport in nanoscale ZnO photocatalytic devices proceeds predominantly within the defect-rich surface region, which may lead to enhanced surface recombination and explain their lower performance compared to titanium dioxide (TiO 2 )-based systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

High-Performance Semiempirical Excited-State Molecular Dynamics Powered by Graphics Processing Units

Here, this Letter introduces excited-state molecular dynamics in PYSEQM, a GPU-accelerated semiempirical quantum chemistry engine implemented in PyTorch. The new module enables Born–Oppenheimer molecular dynamics (BOMD) using configuration-interaction singles and random phase approximation for excited states, allowing long trajectories and large statistical ensembles to be simulated efficiently on a single GPU. We also implement an extended Lagrangian excited-state BOMD (XL-ESMD) scheme that propagates auxiliary electronic variables, enabling relaxed ground and excited-state convergence thresholds without compromising energy conservation. The excited-state BOMD implementation scales smoothly from small chromophores to a nearly 900-atom dendrimer (taking 6.5 s per MD step). PYSEQM also supports batched execution, allowing many geometries or trajectories to be evaluated in a single GPU launch, substantially increasing throughput and making ensemble-based protocols routine. As a demonstration, we compute absorption, emission, and infrared spectra from trajectories propagated on the ground and first excited states. The XL-ESMD scheme yields identical spectra at significantly lower computational cost, establishing the role of extended Lagrangian based dynamics for efficient excited-state BOMD simulations. Beyond raw performance, PYSEQM’s PyTorch foundation provides automatic differentiation for forces, efficient GPU batching, and seamless interfacing with machine learning models. These capabilities position PYSEQM as a practical platform for machine learning-augmented excited-state dynamics and lay the foundation for future data-driven nonadiabatic excited-state dynamics modeling of ultrafast spectroscopic probes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Recent Advances in Immobilizing and Benchmarking Molecular Catalysts for Artificial Photosynthesis

Transition metal complexes have been widely used as catalysts or chromophores in artificial photosynthesis. Traditionally, they are employed in homogeneous settings. Despite their functional versatility and structural tunability, broad industrial applications of these catalysts are impeded by the limitations of homogeneous catalysis such as poor catalyst recyclability, solvent constraints (mostly organic solvents), and catalyst durability. Over the past few decades, researchers have developed various methods for molecular catalyst heterogenization to overcome these limitations. Here, in this review, we summarize recent developments in heterogenization strategies, with a focus on describing methods employed in the heterogenization process and their effects on catalytic performances. Alongside the in-depth discussion of heterogenization strategies, this review aims to provide a concise overview of the key metrics associated with heterogenized systems. We hope this review will aid researchers who are new to this research field in gaining a better understanding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Visible-Light Photoinitiation of (Meth)acrylate Polymerization with Autonomous Post-Conversion

Conversion plateaus rapidly in radical photopolymerizations (RPPs) following discontinuation of irradiation due to rapid termination of reactive radicals, which restricts the wider use of RPPs in applications that involve nonuniform light access including those with attenuated light transmission or irregular surfaces. Based on our recent report of a radical dark-curing photoinitiator (DCPI) that continues polymerization beyond the cessation of irradiation by enabling latent redox initiation with photo-released amine in the presence of a suitable oxidant, we developed a new DCPI with an absorption spectrum that extends well into the visible range. Our design process involved a series of computational investigations of candidate molecules, including a systematic study of substituents and their position-dependent effects on absorption characteristics, electronic transitions, and the photochemical mechanism and its associated energetics. Our quantum chemical computations identified the target compound 5,7-dimethoxy-6-bromo-3-aroylcoumarin-DMPT/BPh4 and predicted that it would facilitate the dark-curing mechanism by concurrent photo-radical generation and photo-induced release of an efficient redox reductant under visible irradiation. This reductant-tethered chromophore was then synthesized and optically characterized with UV–vis spectroscopy that revealed its strong visible-light absorption with a molar absorptivity of 5710 M–1 cm–1 at 405 nm and 50 M–1 cm–1 at 455 nm. We then demonstrated extensive dark-curing of >35% additional conversion over 25 min following brief activation of the shelf-stable one-part system by irradiation with a 455 nm LED that was ceased at 20% conversion. In contrast, shuttering irradiation of the control formulation at that same point resulted in immediate cessation of conversion, which plateaued at 20%. We determined a remarkable initiator efficiency of 2.82 that results from the additional redox-generated radicals with a 77% photo-reductant generation quantum yield. The combination of superior photo- and dark-curing efficiencies of this new visible DCPI is expected to open new application opportunities in RPP, especially those involving resins that are highly light attenuating, surfaces that possess irregular features that produce uneven irradiance, and production lines where continued dark-curing downstream of the light activation step enhances line efficiencies.

absorption spectrum↗
DOE OSTI2020

Imaging Supramolecular Morphogenesis with Confocal Laser Scanning Microscopy at Elevated Temperatures

The morphogenesis of supramolecular assemblies is a highly dynamic process that has only recently been recognized, and our understanding of this phenomenon will require imaging techniques capable of crossing scales. Shape transformations depend both on the complex energy landscapes of supramolecular systems and the kinetically controlled pathways that define their structures and functions. We report here the use of confocal laser scanning microscopy coupled with a custom-designed variable-temperature sample stage that enables in situ observation of such shape changes. The submicrometer resolution of this technique allows for real-time observation of the nanostructures in the native liquid environments in which they transform with thermal energy. We use this technique to study the temperature-dependent morphogenic behavior of peptide amphiphile nanofibers and photocatalytic chromophore amphiphile nanoribbons. Furthermore, the variable-temperature confocal microscopy technique demonstrated in this work can sample a large volume and provides real-time information on thermally induced morphological changes in the solution.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Site-Selective Modification of Lanthanum Oxychloride to Modulate Halide-Ion Conduction

Design principles for solid-state halide-ion conduction remain poorly defined despite the increasing importance of halide ions as charge carriers in a variety of energy storage and electrochemical computing technologies. Here, we employ a siteselective modification strategy in which aliovalent cations are preferentially introduced at the La 3+ crystallographic site of LaOCl in the 2c Wyckoff position, enabling controlled generation of chloride vacancies and modification of lattice dynamics to enhance chloride-ion conductivity. Aliovalent substitution of La 3+ with Mg 2+ , Ca 2+ , and Sr 2+ generates charge-compensating Cl vacancies while preserving the matlockite crystal structure. X-ray excited optical luminescence measurements with Dy 3+ as a reporter chromophore evidence vacancy-derived midgap electronic states and an extended energy range of radiation-less Auger electron emission corresponding to substantial modification of electronic structure and local electrostatic potentials. Ca alloying at 8−10 at. % increases the chloride-ion conductivity by three- to 4 orders of magnitude as compared to unalloyed LaOCl, whereas comparable amounts of Sr- and Mg-alloying in LaOCl imbue less pronounced conductivity enhancements. Temperature-dependent Raman spectroscopy measurements reveal that Ca- and Sr-alloying substantially soften the La−Cl sublattice and yield a more compliant crystal lattice that can deform to accommodate Cl-ion migration. Structure solutions derived from Rietveld refinements to powder Xray diffraction reveal larger O−La−Cl bond-angle deviations and enhanced out-of-plane cation displacements for Ca- and Sr-alloyed compositions as compared to Mg-alloyed LaOCl. Such local distortions enhance chloride-ion mobility by reshaping and flattening vacancy migration energy landscapes and by modulating lattice dynamics governing anion conduction. We further illustrate that coalloying of Ca with Mg and Sr induces a nonmonotonic conductivity−defect stoichiometry relationship that can be rationalized based on cooperative interactions. Together, these results establish site-selective aliovalent alloying of LaOCl as an effective route to halide-ion solid electrolytes and provide broadly generalizable design principles for site-selective modification to induce vacancy formation and lattice softening to engender facile anion transport

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Electro-Optic Modulation Using Metal-Free Perovskites

Electro-optic (EO) modulation is of interest to impart information onto an optical carrier. Inorganic crystals—most notably LiNbO 3 and BaTiO 3 —exhibit EO modulation and good stability, but are difficult to integrate with silicon photonic technology. Solution-processed organic EO materials are readily integrated but suffer from thermal degradation at the temperatures required in operating conditions for accelerated reliability studies. Hybrid organic–inorganic metal halide perovskites have the potential to overcome these limitations; however, these have so far relied on heavy metals such as lead and cadmium. Here, we report linear EO modulation using metal-free perovskites, which maintain the crystalline features of the inorganic EO materials and incorporate the flexible functionality of organic EO chromophores. We find that, by introducing a deficiency of cations, we reduce the symmetry in the perovskite crystal and produce thereby an increased EO response. The best-engineered perovskites reported herein showcase an EO coefficient of 14 pm V –1 at a modulation frequency of 80 kHz, an order of magnitude higher than in the nondefective materials. Furthermore, we observe split peaks in the X-ray diffraction and neutron diffraction patterns of the defective sample, indicating that the crystalline structure has been distorted and the symmetry reduced. Density functional theory (DFT) studies link this decreased symmetry to NH 4 + deficiencies. This demonstration of EO from metal-free perovskites highlights their potential in next-generation optical information transmission.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Sequential Infiltration Synthesis (SIS) of In 2 O 3 -Based Porous Photoelectrodes for Molecular Sensitization

High-surface-area photoelectrodes are highly desirable for solar energy conversion applications, particularly in systems where surface-bound molecular chromophores are responsible for light absorption. To this end, porous Indium-Zinc-Oxide (IZO) frameworks are fabricated via Sequential Infiltration Synthesis (SIS) into poly(methyl methacrylate) (PMMA) films followed by air annealing. A more complete understanding of the multimetal infiltration process conditions and postannealing temperature allows for precise control of zinc (Zn) incorporation to afford porous, conductive, transparent, and amorphous photoelectrodes. Uniform incorporation of both indium (In) and Zn is found to require extended diethylzinc (DEZ) exposures to compensate for remarkably slow precursor diffusion in the presence of indium oxyhydroxide nuclei. SIS-fabricated IZO photoelectrodes are structurally robust, electrochemically active, and exhibit dye adsorption that suggest practical surface area enhancements greater than 100×. In conclusion, these attributes establish SIS as a rapid, scalable, and reproducible route to photoelectrodes for solar energy conversion and hybrid interface characterization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

“Antenna-like” Light-Harvesting in Partially Metalated Porphyrin Hydrogen-Bonded Organic Frameworks

Arrays of light harvesting molecules with long-range order hold promise as materials capable of efficient collection of photons as well as rapid transport of captured solar energy to chemical catalysts. Hydrogen-bonded organic frameworks (HOFs) could be promising artificial light-harvesting platforms, due to their crystalline nature and their comparative ease of synthesis. In this work, mixed-linkers of either zinc-metallated or free base tetrakis(4-carboxyphenyl)porphyrin HOFs were examined and found to demonstrate ‘antenna-like’ light harvesting behavior. Using time-resolved emission spectroscopy, Förster resonance energy transfer from zinc porphyrin to free-base porphyrin was assessed. Based on changes in the emission peak profile as the ratio of zinc porphyrin to free-base porphyrin is varied, we find that, in the limit of 100% zinc porphyrin, a photogenerated exciton can sample ~48 chromophores. These findings suggest that stacked linkers within HOFs can act as light harvesting ‘antennae’ and with encapsulation of suitable catalysts, may offer prospective application as photochemical energy conversion systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Mechanistic Insights into Visible-Light-Induced ATRA Reactions Powered by the Symbiotic Relationship between Cu(II)/Cu(I) Phenanthroline Complexes

As photoredox catalysis continues to yield promising chemical transformations, there is an increased need to understand how specific photocatalysts function to improve reaction efficiencies while expanding their scope. Copper-phenanthroline-based photocatalysts such as Cu II (dap)Cl 2 (dap = 2,9-di(p-anisyl)-1,10-phenanthroline) and [Cu I (dap) 2 ]Cl were both found to be equally capable of olefin activation through electrophilic atom transfer radical addition (ATRA) reactions. Although these molecular catalysts have proven successful, many intermediates suggested in the proposed catalytic cycles have never been detected. One undetermined aspect in this chemistry is related to how one equivalent of Cu II (dap)Cl 2 generates half of an equivalent of [Cu I (dap) 2 ] + during the photocatalytic sequence. To this end, we initially used more synthetically accessible model systems, namely, [Cu I (dpp) 2 ]Cl and Cu II (dpp)Cl 2 (dpp = 2,9-diphenyl-1,10-phenanthroline), to glean detailed mechanistic insights into this unusual symbiotic relationship. We directly detected several intermediates involved in the ATRA photocatalytic cycle using these model chromophores in conjunction with electronic spectroscopy, infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) mass spectrometry, electronic structure calculations, EPR spin-trap experiments, and 1 H NMR spectroscopy. We found that the unique ligand lability and coordinating properties of acetonitrile enable both the in situ oxidation of [Cu I (dpp) 2 ] + by tosyl chloride into Cu II (dpp)Cl 2 and the visible-light-induced homolysis of the Cu II –Cl bond, which initiates the conversion to the Cu I species [Cu I (dpp) 2 ][Cu I Cl 2 ]. Here, the combined findings from the present study of the catalytic cycle demonstrate that the symbiotic relationship between Cu II (dpp)Cl 2 and [Cu I (dpp) 2 ] + , as well as between Cu II (dap)Cl 2 and [Cu I (dap) 2 ] + , is the critical factor enabling the ATRA photoreaction by departing from either photocatalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Controllable Phycobilin Modification: An Alternative Photoacclimation Response in Cryptophyte Algae

Cryptophyte algae are well-known for their ability to survive under low light conditions using their auxiliary light harvesting antennas, phycobiliproteins. Mainly acting to absorb light where chlorophyll cannot (500-650 nm), phycobiliproteins also play an instrumental role in helping cryptophyte algae respond to changes in light intensity through the process of photoacclimation. Until recently, photoacclimation in cryptophyte algae was only observed as a change in the cellular concentration of phycobiliproteins; however, an additional photoacclimation response was recently discovered that causes shifts in the phycobiliprotein absorbance peaks following growth under red, blue, or green light. Here, we reproduce this newly identified photoacclimation response in two species of cryptophyte algae and elucidate the origin of the response on the protein level. We compare isolated native and photoacclimated phycobiliproteins for these two species using spectroscopy and mass spectrometry, and we report the X-ray structures of each phycobiliprotein and the corresponding photoacclimated complex. We find that neither the protein sequences nor the protein structures are modified by photoacclimation. We conclude that cryptophyte algae change one chromophore in the phycobiliprotein β subunits in response to changes in the spectral quality of light. Ultrafast pump-probe spectroscopy shows that the energy transfer is weakly affected by photoacclimation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Amplified Spontaneous Emission from Electron–Hole Quantum Droplets in Colloidal CdSe Nanoplatelets

Two-dimensional cadmium selenide nanoplatelets (NPLs) exhibit large absorption cross sections and homogeneously broadened band-edge transitions that offer utility in wide-ranging optoelectronic applications. Here, we examine the temperature-dependence of amplified spontaneous emission (ASE) in 4- and 5-monolayer thick NPLs and show that the threshold for close-packed (neat) films decreases with decreasing temperature by a factor of 2-10 relative to ambient temperature owing to extrinsic (trapping) and intrinsic (phonon-derived line width) factors. Interestingly, for pump intensities that exceed the ASE threshold, we find development of intense emission to lower energy in particular provided that the film temperature is <= 200 K. For NPLs diluted in an inert polymer, both biexcitonic ASE and low-energy emission are suppressed, suggesting that described neat-film observables rely upon high chromophore density and rapid, collective processes. Transient emission spectra reveal ultrafast red-shifting with the time of the lower energy emission. Taken together, these findings indicate a previously unreported process of amplified stimulated emission from polyexciton states that is consistent with quantum droplets and constitutes a form of exciton condensate. For studied samples, quantum droplets form provided that roughly 17 meV or less of thermal energy is available, which we hypothesize relates to polyexciton binding energy. Polyexciton ASE can produce pump-fluence-tunable red-shifted ASE even 120 meV lower in energy than biexciton ASE. Finally, our findings convey the importance of biexciton and polyexciton populations in nanoplatelets and show that quantum droplets can exhibit light amplification at significantly lower photon energies than biexcitonic ASE.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Tunable Spin Qubit Pairs in Quantum Dot–Molecule Conjugates

Organic molecules and quantum dots (QDs) have both shown promise as materials that can host quantum bits (qubits). This is in part because of their synthetic tunability. The current work employs a combination of both materials to demonstrate a series of tunable quantum dot–organic molecule conjugates that can both host photogenerated spin-based qubit pairs (SQPs) and sensitize molecular triplet states. The photogenerated qubit pairs, composed of a spin-correlated radical pair (SCRP), are particularly intriguing since they can be initialized in well-defined, nonthermally populated, quantum states. Additionally, the radical pair enables charge recombination to a polarized molecular triplet state, also in a well-defined quantum state. The materials underlying this system are an organic molecular chromophore and electron donor, 9,10-bis(phenylethynyl)anthracene, and a quantum dot acceptor composed of ZnO. We prepare a series of quantum dot–molecule conjugates that possess variable quantum dot size and two different linker lengths connecting the two moieties. Optical spectroscopy revealed that the QD–molecule conjugates undergo photoexcited charge separation to generate long-lived charge-separated radical pairs. The resulting spin states are probed using light-induced time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy, revealing the presence of singlet-generated SCRPs and molecular triplet states. Notably, the EPR spectra of the radical pairs are dependent on the geometry of this highly tunable system. The g value of the ZnO QD anion is size tunable, and the line widths are influenced by radical pair separation. Overall, this work demonstrates the power of synthetic tunability in adjusting the spin specific addressability, satisfying a key requirement of functional qubit systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Storage-Induced Collapse of Lignin Macromolecular Structure and Its Impacts on the Biorefinery

Lignin plays a vital role in the economics of biorefineries, serving as a source of process energy and a feedstock for sustainable fuels and chemical production. While understanding lignin’s chemical composition is crucial, emerging evidence suggests that a more comprehensive understanding of its macromolecular structure is critical to explaining its complex behavior in the biorefinery. This study investigated the partial collapse of the lignin network in corn stover feedstock after harvest and storage as a result of the microbial digestion of hemicellulose. Fluorescence microscopy was used to detect the collapse of lignin in terms of lignin’s inter-molecular interaction and the re-orientation of lignin’s chromophores, by the changes in lignin’s fluorescence lifetime, anisotropy, and the number of effective emitters. With minimal sample perturbation, our in-situ microscopic results revealed lignin's coil-globule transition phenomena, which was only previously predicted by molecular dynamics modeling extracted lignin in solvent. This collapse of lignin macromolecular structure was confirmed by results from NMR, IR, Raman, and powder X-ray diffraction. We also investigated the impact of this storage-induced collapse on the downstream biorefinery processes. Our study revealed that the two major approaches for lignin valorization in the lignin-first biorefinery model, namely monomer extraction and milled wood lignin extraction, were negatively impacted by the lignin collapse. As changes during storage are a source of feedstock variability, our study highlights the importance of understanding the effect of feedstock handling on biorefinery operations and economics.

09 BIOMASS FUELS↗
DOE OSTI2020

Improving Energy Transfer within Metal–Organic Frameworks by Aligning Linker Transition Dipoles along the Framework Axis

Crystalline metal-organic frameworks (MOFs) can assemble chromophoric molecules into a wide range of spatial arrangements, which are controlled by the MOF topology. Like natural light-harvesting complexes (LHCs), the precise arrangement modulates interchromophoric interactions, in turn determining excitonic behavior and migration dynamics. To unveil the key factors that control efficient exciton displacements within MOFs, we first developed linkers with low electronic symmetry (as defined by large transition dipoles) and then assembled them into MOFs. These linkers possess extended conjugation along one molecular axis, engendering low optical bandgaps and improved oscillator strength for their lowest-energy transition (S 0 → S 1 ). This enhances absorption-emission spectral overlap and boosts the efficiency of Forster resonance energy transfer, which was observed experimentally by a sizable decrease in emission quantum yield (QY), accompanied by a faster population decay profile. We find that MOFs that orient these elongated linkers along their asymmetric pore channel, e.g., the hexagonal pores in an xly network, manifested >50% decrease in their emission QY with faster decay profiles relative to their corresponding solution dissolved linkers. This is due to an efficient migration of photogenerated excitons at the crystallite peripheral sites to internal sites, which was facilitated by polarized absorption-emission overlap among the parallelly aligned linkers. In contrast, symmetric MOFs, such as those with sqc-a topological net, orient elongated linkers along two perpendicular crystal axes, which hinders efficient exciton migration. This study underscores that MOFs are promising to develop artificial LHCs, but that to achieve an efficient exciton displacement, appropriate topology-guided assembly is required to fully realize the true potential of linkers with low electronic symmetry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Superradiance and Directional Exciton Migration in Metal–Organic Frameworks

Crystalline metal–organic frameworks (MOFs) are promising synthetic analogues of photosynthetic light-harvesting complexes (LHCs). The precise assembly of linkers (organic chromophores) around the topology-defined pores offers the evolution of unique photophysical behaviors that are reminiscence of LHCs. These include MOF excited states with photoabsorbed energy that is spatially dispersed over multiple linkers defining the molecular excitons. The multilinker molecular excitons display superradiance–a hallmark of coupled oscillators seen in LHCs–with radiative rate constant (k rad ) exceeding that of a single linker. Our theoretical model and experimental results on three zirconium MOFs, namely, PCN-222(Zn), NU-1000, and SIU-100, with similar topology but varying linkers suggest that the size of such molecular excitons depends on the electronic symmetry of the linker. This multilinker exciton model effectively predicts the energy transfer rate constant; corresponding single-step exciton hopping time, ranging from a few picoseconds in SIU-100 and NU-1000 to a few hundreds of picoseconds in PCN-222(Zn), matches well with the experimental data. The model also predicts the anisotropy of exciton displacement with preferential migration along the crystallographic c-axis. Overall, these findings establish various missing links defining the exciton size and dynamics in MOF-assembled linkers. Furthermore, the understandings will provide design principles, especially, positioning the catalysts or electrode relative to the linker orientation for low-density solar energy conversion systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗