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.

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.

Breaking the photoswitch speed limit.

The forthcoming generation of materials, including artificial muscles, recyclable and healable systems, photochromic heterogeneous catalysts, or tailorable supercapacitors, relies on the fundamental concept of rapid switching between two or more discrete forms in the solid state. Herein, we report a breakthrough in the "speed limit" of photochromic molecules on the example of sterically-demanding spiropyran derivatives through their integration within solvent-free confined space, allowing for engineering of the photoresponsive moiety environment and tailoring their photoisomerization rates. The presented conceptual approach realized through construction of the spiropyran environment results in ~1000 times switching enhancement even in the solid state compared to its behavior in solution, setting a record in the field of photochromic compounds. Moreover, integration of two distinct photochromic moieties in the same framework provided access to a dynamic range of rates as well as complementary switching in the material's optical profile, uncovering a previously inaccessible pathway for interstate rapid photoisomerization.

Thermal Conductivity of Covalent-Organic Frameworks.

Covalent-organic frameworks (COFs) are a highly promising class of materials that can provide an excellent platform for thermal management applications. In this Perspective, we first review previous works on the thermal conductivities of COFs. Then we share our insights on achieving high, low, and switchable thermal conductivities of future COFs. To obtain the desired thermal conductivity, a comprehensive understanding of their thermal transport mechanisms is necessary but lacking. We discuss current limitations in atomistic simulations, synthesis, and thermal conductivity measurements of COFs and share potential pathways to overcoming these challenges. We hope to stimulate collective, interdisciplinary efforts to study the thermal conductivity of COFs and enable their wide range of thermal applications.

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.

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.

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.

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.

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.

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.

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.

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.

Graphitic supramolecular architectures based on corannulene, fullerene, and beyond.

In this Feature Article, we survey the advances made in the field of fulleretic materials over the last five years. Merging the intriguing characteristics of fulleretic molecules with hierarchical materials can lead to enhanced properties of the latter for applications in optoelectronic, biomaterial, and heterogeneous catalysis sectors. As there has been significant growth in the development of fullerene- and corannulene-containing materials, this article will focus on studies performed during the last five years exclusively, and highlight the recent trends in designing fulleretic compounds and understanding their properties, that has enriched the repertoire of carbon-rich functional materials.

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.

Beyond structural motifs: the frontier of actinide-containing metal-organic frameworks.

In this perspective, we feature recent advances in the field of actinide-containing metal-organic frameworks (An-MOFs) with a main focus on their electronic, catalytic, photophysical, and sorption properties. This discussion deviates from a strictly crystallographic analysis of An-MOFs, reported in several reviews, or synthesis of novel structural motifs, and instead delves into the remarkable potential of An-MOFs for evolving the nuclear waste administration sector. Currently, the An-MOF field is dominated by thorium- and uranium-containing structures, with only a few reports on transuranic frameworks. However, some of the reported properties in the field of An-MOFs foreshadow potential implementation of these materials and are the main focus of this report. Thus, this perspective intends to provide a glimpse into the challenges, triumphs, and future directions of An-MOFs in sectors ranging from the traditional realm of gas sorption and separation to recently emerging areas such as electronics and photophysics.

"Broken-hearted" carbon bowl via electron shuttle reaction: energetics and electron coupling.

Unprecedented one-step C[double bond, length as m-dash]C bond cleavage leading to opening of the buckybowl (π-bowl), that could provide access to carbon-rich structures with previously inaccessible topologies, is reported; highlighting the possibility to implement drastically different synthetic routes to π-bowls in contrast to conventional ones applied for polycyclic aromatic hydrocarbons. Through theoretical modeling, we evaluated the mechanistic pathways feasible for π-bowl planarization and factors that could affect such a transformation including strain and released energies. Through employment of Marcus theory, optical spectroscopy, and crystallographic analysis, we estimated the possibility of charge transfer and electron coupling between "open" corannulene and a strong electron acceptor such as 7,7,8,8-tetracyanoquinodimethane. Alternative to a one-pot solid-state corannulene "unzipping" route, we reported a nine-step solution-based approach for preparation of novel planar "open" corannulene-based derivatives in which electronic structures and photophysical profiles were estimated through the energies and isosurfaces of the frontier natural transition orbitals.