Mining for Metal-Organic Systems: Chemistry Frontiers of Th-, U-, and Zr-Materials.

The conceptual framework presented in this Perspective overviews the design principles of innovative thorium-based materials that could address urgent needs of the medicinal, nuclear energy, and waste remediation sectors from the lens of zirconium and uranium analogs. We survey the intersections of Zr, Th, and U chemistry with a focus on how the intrinsic behavior of each metal translates to broader material properties, including, but not limited to, structural and topological diversity, preferential metal-ligand binding, and reactivity. On the example of several classes of materials, including organometallic complexes, polyoxometalates, and the primary focus of this Perspective, metal-organic frameworks (MOFs), the design principles that govern the preparation of Zr-, Th-, and U-compounds, including oxophilicity, variation in oxidation states, and stable coordination environments have been considered. Further, we highlight how the impact of the mentioned variables may shift throughout the progression from discrete molecular systems to extended structures. We discuss the common assumption that zirconium-organic materials are typically considered a close analog of thorium-based congeners in areas such as material design and preparation. Through consideration of fundamental chemistry principles, we shed light on the relationships between Zr-, Th-, and U-based materials and highlight how a critical analysis of their distinct properties can be used to target a desired material performance. As a result, we provide a detailed understanding of Th-based materials chemistry by anchoring their fundamental properties between two well-studied reference points, zirconium- and uranium-containing analogs.

Friends or Foes: Fundamental Principles of Th-Organic Scaffold Chemistry Using Zr-Analogs as a Guide.

The fundamental interest in actinide chemistry, particularly for the development of thorium-based materials, is experiencing a renaissance owing to the recent and rapidly growing attention to fuel cycle reactors, radiological daughters for nuclear medicine, and efficient nuclear stockpile development. Herein, we uncover fundamental principles of thorium chemistry on the example of Th-based extended structures such as metal-organic frameworks in comparison with the discrete systems and zirconium extended analogs, demonstrating remarkable over two-and-half-year chemical stability of Th-based frameworks as a function of metal node connectivity, amount of defects, and conformational linker rigidity through comprehensive spectroscopic and crystallographic analysis as well as theoretical modeling. Despite exceptional chemical stability, we report the first example of studies focusing on the reactivity of the most chemically stable Th-based frameworks in comparison with the discrete Th-based systems such as metal-organic complexes and a cage, contrasting multicycle recyclability and selectivity (>97%) of the extended structures in comparison with the molecular compounds. Overall, the presented work not only establishes the conceptual foundation for evaluating the capabilities of Th-based materials but also represents a milestone for their multifaceted future and foreshadows their potential to shape the next era of actinide chemistry.

Photochromic Ln-MOFs: A Platform for Metal-Photoswitch Cooperativity.

Optoelectronic devices based on lanthanide-containing materials are an emergent area of research due to imminent interest in a new generation of diode materials, optical and magnetic sensors, and ratiometric thermometers. Tailoring material properties through the employment of photo- or thermochromic moieties is a powerful approach that requires a deep fundamental understanding of possible cooperativity between lanthanide-based metal centers and integrated switchable units. In this work, we probe this concept through the synthesis, structural analysis, and spectroscopic characterization of novel photochromic lanthanide-based metal-organic materials containing noncoordinatively integrated photoresponsive 4,4'-azopyridine between lanthanide-based metal centers. As a result, a photophysical material response tailored on demand through the incorporation of photochromic compounds within a rigid matrix was investigated. The comprehensive analysis of photoresponsive metal-organic materials includes single-crystal X-ray diffraction and diffuse reflectance spectroscopic studies that provide guiding principles necessary for understanding photochromic unit-lanthanide-based metal-organic framework (MOF) cooperativity. Furthermore, steady-state and time-resolved diffuse reflectance spectroscopic studies revealed a rapid rate of photoresponsive moiety attenuation upon its integration within the rigid matrix of lanthanide-based MOFs in comparison with that in solution, highlighting a unique role and synergy that occurred between stimuli-responsive moieties and the lanthanide-based MOF platform, allowing for tunability and control of material photoisomerization kinetics.

GFP-related chromophores: photoisomerization, thermal reversion, and DNA labelling.

Due to the pronounced effect of the confined environment on the photochemical properties of 4-hydroxybenzylidene imidazolinone (HBI), a GFP-related chromophore, imidazolidinone and imidazothiazolone analogues have been studied as fluorescent probes. Their photoisomerization and their thermal reversion were studied under 365-nm-irradiation, resulting in observation of an enthalpy-entropy compensation effect. Theoretical studies were carried out to shed light on the thermal reversion mechanism. Moreover, photophysical studies of benzylidene imidazothiazolone in the presence of dsDNA revealed fluorescence enhancement. The prepared compounds could be considered as a valuable tool for the detailed investigation of physicochemical, biochemical, or biological systems.

Traffic Lights for Catalysis: Stimuli-Responsive Molecular and Extended Catalytic Systems.

The advances made in the field of stimuli-responsive catalysis during the last five years with a focus on the novel recently-emerged directions and applications have been surveyed. Metal-free catalysts and organometallic complexes, as well as biomimetic systems and extended structures, which display switchable catalytic activity for a variety of organic transformations, are discussed. Light-activated systems comprised of photochromic molecules capable of modulating reaction rate, yield, or enantioselectivity based on geometric and electronic changes associated with photoisomerization are the focus of the detailed discussion. Alternative stimuli, including pH and temperature, which could be applied either alone or in combination with light, are also addressed. Recent advances clearly demonstrate that the capability to finely tune catalyst behavior via an external stimulus is a powerful tool that could alter the landscape of sustainable chemistry.

Cooperative and Orthogonal Switching in the Solid State Enabled by Metal-Organic Framework Confinement Leading to a Thermo-Photochromic Platform.

Cooperative behavior and orthogonal responses of two classes of coordinatively integrated photochromic molecules towards distinct external stimuli were demonstrated on the first example of a photo-thermo-responsive hierarchical platform. Synergetic and orthogonal responses to temperature and excitation wavelength are achieved by confining the stimuli-responsive moieties within a metal-organic framework (MOF), leading to the preparation of a novel photo-thermo-responsive spiropyran-diarylethene based material. Synergistic behavior of two photoswitches enables the study of stimuli-responsive resonance energy transfer as well as control of the photoinduced charge transfer processes, milestones required to advance optoelectronics development. Spectroscopic studies in combination with theoretical modeling revealed a nonlinear effect on the material electronic structure arising from the coordinative integration of photoresponsive molecules with distinct photoisomerization mechanisms. Thus, the reported work covers multivariable facets of not only fundamental aspects of photoswitch cooperativity, but also provides a pathway to modulate photophysics and electronics of multidimensional functional materials exhibiting thermo-photochromism.

Confinement-Driven Photophysics in Hydrazone-Based Hierarchical Materials.

Confinement-imposed photophysics was probed for novel stimuli-responsive hydrazone-based compounds demonstrating a conceptual difference in their behavior within 2D versus 3D porous matrices for the first time. The challenges associated with photoswitch isomerization arising from host interactions with photochromic compounds in 2D scaffolds could be overcome in 3D materials. Solution-like photoisomerization rate constants were realized for sterically demanding hydrazone derivatives in the solid state through their coordinative immobilization in 3D scaffolds. According to steady-state and time-resolved photophysical measurements and theoretical modeling, this approach provides access to hydrazone-based materials with fast photoisomerization kinetics in the solid state. Fast isomerization of integrated hydrazone derivatives allows for probing and tailoring resonance energy transfer (ET) processes as a function of excitation wavelength, providing a novel pathway for ET modulation.

f-block MOFs: A Pathway to Heterometallic Transuranics.

A novel series of heterometallic f-block-frameworks including the first examples of transuranic heterometallic 238 U/239 Pu-metal-organic frameworks (MOFs) and a novel monometallic 239 Pu-analog are reported. In combination with theoretical calculations, we probed the kinetics and thermodynamics of heterometallic actinide(An)-MOF formation and reported the first value of a U-to-Th transmetallation rate. We concluded that formation of uranyl species could be a driving force for solid-state metathesis. Density of states near the Fermi edge, enthalpy of formation, band gap, proton affinity, and thermal/chemical stability were probed as a function of metal ratios. Furthermore, we achieved 97 % of the theoretical maximum capacity for An-integration. These studies shed light on fundamental aspects of actinide chemistry and also foreshadow avenues for the development of emerging classes of An-containing materials, including radioisotope thermoelectric generators or metalloradiopharmaceuticals.

Metal-Photoswitch Friendship: From Photochromic Complexes to Functional Materials.

Cooperative metal-photoswitch interfaces comprise an application-driven field which is based on strategic coupling of metal cations and organic photochromic molecules to advance the behavior of both components, resulting in dynamic molecular and material properties controlled through external stimuli. In this Perspective, we highlight the ways in which metal-photoswitch interplay can be utilized as a tool to modulate a system's physicochemical properties and performance in a variety of structural motifs, including discrete molecular complexes or cages, as well as periodic structures such as metal-organic frameworks. This Perspective starts with photochromic molecular complexes as the smallest subunit in which metal-photoswitch interactions can occur, and progresses toward functional materials. In particular, we explore the role of the metal-photoswitch relationship for gaining fundamental knowledge of switchable electronic and magnetic properties, as well as in the design of stimuli-responsive sensors, optically gated memory devices, catalysts, and photodynamic therapeutic agents. The abundance of stimuli-responsive systems in the natural world only foreshadows the creative directions that will uncover the full potential of metal-photoswitch interactions in the coming years.

Stimuli-Modulated Metal Oxidation States in Photochromic MOFs.

Tuning metal oxidation states in metal-organic framework (MOF) nodes by switching between two discrete linker photoisomers via an external stimulus was probed for the first time. On the examples of three novel photochromic copper-based frameworks, we demonstrated the capability of switching between +2 and +1 oxidation states, on demand. In addition to crystallographic methods used for material characterization, the role of the photochromic moieties for tuning the oxidation state was probed via conductivity measurements, cyclic voltammetry, and electron paramagnetic resonance, X-ray photoelectron, and diffuse reflectance spectroscopies. We confirmed the reversible photoswitching activity including photoisomerization rate determination of spiropyran- and diarylethene-containing linkers in extended frameworks, resulting in changes in metal oxidation states as a function of alternating excitation wavelengths. To elucidate the switching process between two states, the photoisomerization quantum yield of photochromic MOFs was determined for the first time. Overall, the introduced noninvasive concept of metal oxidation state modulation on the examples of stimuli-responsive MOFs foreshadows a new pathway for alternation of material properties toward targeted applications.

Capture Instead of Release: Defect-Modulated Radionuclide Leaching Kinetics in Metal-Organic Frameworks.

Comparison of defect-controlled leaching-kinetics modulation of metal-organic frameworks (MOFs) and porous functionalized silica-based materials was performed on the example of a radionuclide and radionuclide surrogate for the first time, revealing an unprecedented readsorption phenomenon. On a series of zirconium-based MOFs as model systems, we demonstrated the ability to capture and retain >99% of the transuranic 241Am radionuclide after 1 week of storage. We report the possibility of tailoring radionuclide release kinetics in MOFs through framework defects as a function of postsynthetically installed organic ligands including cation-chelating crown ether-based linkers. Based on comprehensive analysis using spectroscopy (EXAFS, UV-vis, FTIR, and NMR), X-ray crystallography (single crystal and powder), and theoretical calculations (nine kinetics models and structure simulations), we demonstrated the synergy of radionuclide integration methods, topological restrictions, postsynthetic scaffold modification, and defect engineering. This combination is inaccessible in any other material and highlights the advantages of using well-defined frameworks for gaining fundamental knowledge necessary for the advancement of actinide-based material development, providing a pathway for addressing upcoming challenges in the nuclear waste administration sector.

Photophysics Modulation in Photoswitchable Metal-Organic Frameworks.

In this Review, we showcase the upsurge in the development and fundamental photophysical studies of more than 100 metal-organic frameworks (MOFs) as versatile stimuli-responsive platforms. The goal is to provide a comprehensive analysis of the field of photoresponsive MOFs while delving into the underlying photophysical properties of various classes of photochromic molecules including diarylethene, azobenzene, and spiropyran as well as naphthalenediimide and viologen derivatives integrated inside a MOF matrix as part of a framework backbone, as a ligand side group, or as a guest. In particular, the geometrical constraints, photoisomerization rates, and electronic structures of photochromic molecules integrated inside a rigid MOF scaffold are discussed. Thus, this Review reflects on the challenges and opportunities of using photoswitchable MOFs in next-generation multifunctional stimuli-responsive materials while highlighting their use in optoelectronics, erasable inks, or as the next generation of sensing devices.

Confinement-guided photophysics in MOFs, COFs, and cages.

In this review, the dependence of the photophysical response of chromophores in the confined environments associated with crystalline scaffolds, such as metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), and molecular cages, has been carefully evaluated. Tunability of the framework aperture, cavity microenvironment, and scaffold topology significantly affects emission profiles, quantum yields, or fluorescence lifetimes of confined chromophores. In addition to the role of the host and its effect on the guest, the methods for integration of a chromophore (e.g., as a framework backbone, capping linker, ligand side group, or guest) are discussed. The overall potential of chromophore-integrated frameworks for a wide-range of applications, including artificial biomimetic systems, white-light emitting diodes, photoresponsive devices, and fluorescent sensors with unparalleled spatial resolution are highlighted throughout the review.

A Metal-Organic Framework (MOF)-Based Multifunctional Cargo Vehicle for Reactive-Gas Delivery and Catalysis.

The efficient delivery of reactive and toxic gaseous reagents to organic reactions was studied using metal-organic frameworks (MOFs). The simultaneous cargo vehicle and catalytic capabilities of several MOFs were probed for the first time using the examples of aromatization, aminocarbonylation, and carbonylative Suzuki-Miyaura coupling reactions. These reactions highlight that MOFs can serve a dual role as a gas cargo vehicle and a catalyst, leading to product formation with yields similar to reactions employing pure gases. Furthermore, the MOFs can be recycled without sacrificing product yield, while simultaneously maintaining crystallinity. The reported findings were supported crystallographically and spectroscopically (e.g., diffuse reflectance infrared Fourier transform spectroscopy), foreshadowing a pathway for the development of multifunctional MOF-based reagent-catalyst cargo vessels for reactive gas reagents as an attractive alternative to the use of toxic pure gases or gas generators.

Photoresponsive frameworks: energy transfer in the spotlight.

In this paper, spiropyran-containing metal- and covalent-organic frameworks (MOFs and COFs, respectively) are probed as platforms for fostering photochromic behavior in solid-state materials, while simultaneously promoting directional energy transfer (ET). In particular, Förster resonance energy transfer (FRET) between spiropyran and porphyrin derivatives integrated as linkers in the framework matrix is discussed. The photochromic spiropyran derivatives allow for control over material optoelectronic properties through alternation of excitation wavelengths. Photoinduced changes in the material electronic profile have also been probed through conductivity measurements. Time-resolved photoluminescence studies were employed to evaluate the effect of photochromic linkers on material photophysics. Furthermore, "forward" and "reverse" FRET processes occurring between two distinct chromophores were modeled, and the Förster critical radii and ET rates were estimated to support the experimentally observed changes in material photoluminescence.

Host-Guest Interactions in a Metal-Organic Framework Isoreticular Series for Molecular Photocatalytic CO2 Reduction.

A strategy to improve homogeneous molecular catalyst stability, efficiency, and selectivity is the immobilization on supporting surfaces or within host matrices. Herein, we examine the co-immobilization of a CO2 reduction catalyst [ReBr(CO)3 (4,4'-dcbpy)] and a photosensitizer [Ru(bpy)2 (5,5'-dcbpy)]Cl2 using the isoreticular series of metal-organic frameworks (MOFs) UiO-66, -67, and -68. Specific host pore size choice enables distinct catalyst and photosensitizer spatial location-either at the outer MOF particle surface or inside the MOF cavities-affecting catalyst stability, electronic communication between reaction center and photosensitizer, and consequently the apparent catalytic rates. These results allow for a rational understanding of an optimized supramolecular layout of catalyst, photosensitizer, and host matrix.

Heterometallic Actinide-Containing Photoresponsive Metal-Organic Frameworks: Dynamic and Static Tuning of Electronic Properties.

Acquiring fundamental knowledge of properties of actinide-based materials is a necessary step to create new possibilities for addressing the current challenges in the nuclear energy and nuclear waste sectors. In this report, we established a photophysics-electronics correlation for actinide-containing metal-organic frameworks (An-MOFs) as a function of excitation wavelength, for the first time. A stepwise approach for dynamically modulating electronic properties was applied for the first time towards actinide-based heterometallic MOFs through integration of photochromic linkers. Optical cycling, modeling of density of states near the Fermi edge, conductivity measurements, and photoisomerization kinetics were employed to shed light on the process of tailoring optoelectronic properties of An-MOFs. Furthermore, the first photochromic MOF-based field-effect transistor, in which the field-effect response could be changed through light exposure, was constructed. As a demonstration, the change in current upon light exposure was sufficient to operate a two-LED fail-safe indicator circuit.

Confinement-Driven Photophysics in Cages, Covalent-Organic Frameworks, Metal-Organic Frameworks, and DNA.

Photophysics tunability through alteration of framework aperture (metal-organic framework (MOF) = variable; guest = constant) was probed for the first time in comparison with previously explored concepts (MOF = constant; guest = variable). In particular, analysis of the confinement effect on a photophysical response of integrated 5-(3-chlorobenzylidene)-2,3-dimethyl-3,5-dihydro-4H-imidazol-4-one (Cl-BI) chromophore allowed us to establish a photophysics-aperture relationship. To shed light on the observed correlation, the framework confined environment was replicated using a molecular cage, Pd6(TPT)4 (TPT = 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine), thus allowing for utilization of crystallography, spectroscopy, and theoretical simulations to reveal the effect a confined space has on the chromophore's molecular conformation (including disruption of strong hydrogen bonding and novel conformer formation) and any associated changes on a photophysical response. Furthermore, the chosen Cl-oHBI@Pd6(TPT)4 (Cl-oHBI = 5-(5-chloro-2-hydroxybenzylidene)-2,3-dimethyl-3,5-dihydro-4H-imidazol-4-one, chromophore) system was applied as a tool for targeted cargo delivery of a chromophore to the confined space of DNA, which resulted in promotion of chromophore-DNA interactions through a well-established intercalation mechanism. Moreover, the developed principles were applied toward utilizing a HBI-based chromophore as a fluorescent probe on the example of macrophage cells. For the first time, suppression of non-radiative decay pathways of a chromophore was tested by anchoring the chromophore to a framework metal node, portending a potential avenue to develop an alternative to natural biomarkers. Overall, these studies are among the first attempts to demonstrate the unrevealed potential of a confined scaffold environment for tailoring a material's photophysical response.

Growth of Crystalline Bimetallic Metal-Organic Framework Films via Transmetalation.

Crystalline films of the Cu3(BTC)2 (BTC3- = 1,3,5-benzenetricarboxylate) metal-organic framework (MOF) have been grown by dip-coating an alumina/Si(111) substrate in solutions of Cu(II) acetate and the organic linker H3BTC. Atomic force microscopy (AFM) experiments demonstrate that the substrate is completely covered by the MOF film, while grazing incidence wide-angle X-ray scattering (GIWAXS) establishes the crystallinity of the films. Forty cycles of dip-coating results in a film that is ∼70 nm thick with a root mean squared roughness of 25 nm and crystallites ranging from 50-160 nm in height. Co2+ ions were exchanged into the MOF framework by immersing the Cu3(BTC)2 films in solutions of CoCl2. By varying the temperature and exchange times, different concentrations of Co were incorporated into the films, as determined by X-ray photoelectron spectroscopy experiments. AFM studies showed that morphologies of the bimetallic films were largely unchanged after transmetalation, and GIWAXS indicated that the bimetallic films retained their crystallinity.

"Boarding-Up": Radiation Damage and Radionuclide Leaching Kinetics in Linker-Capped Metal-Organic Frameworks.

For the first time, we report the ability to control radionuclide species release kinetics in metal-organic frameworks (MOFs) as a function of postsynthetic capping linker installation, which is essential for understanding MOF potential as viable radionuclide wasteform materials or versatile platforms for sensing, leaching, and radionuclide sequestration. The radiation damage of prepared frameworks under γ radiation has also been studied. We envision that the presented studies are the first steps toward utilization of the reported scaffolds for more efficient nuclear waste administration.