Kinetic Trapping of Photoluminescent Frameworks During High-Concentration Synthesis of Nonemissive Metal–Organic Frameworks

Halder, Arjun; Bain, David C.; Pitt, Tristan A.; Shi, Zixiao; Oktawiec, Julia; Lee, Jung-Hoon; Tsangari, Stavrini; Ng, Marcus; Fuentes-Rivera, José J.; Forse, Alexander C.; Runčevski, Tomče; Muller, David A.; Musser, Andrew J.; Milner, Phillip J.

doi:10.1021/acs.chemmater.3c02121

Cited by 5 publications

(2 citation statements)

References 79 publications

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“…Broad chemical and thermal stability is one of the highly sought-after traits in the field of metal–organic frameworks (MOFs − ), which shapes the landscape of possible applications with a main focus on specific MOF classes, including those based on zirconium. − Indeed, Zr-MOFs (e.g., possessing fcu- , and ftw-type , topologies) exhibit excellent thermostability up to 500 °C, possess chemical stability across a wide pH range from 2 to 12, and demonstrate exceptional resilience even under 423 Gy/min γ radiation . At the same time, the recent and rapidly growing interest in the development of fuel cycle reactors, radiological daughters for nuclear medicine, and efficient nuclear stockpile recycling serves as the driving force for translating the wealth of fundamental knowledge acquired for Zr-MOFs to thorium-based analogs. − Since the onset of research focusing on Th-based materials, Zr-frameworks have been considered to be the closest analogs due to the shared metal oxidation state (+4), high Lewis acidity, formation of strong coordination bonds to carboxylate-based organic linkers, and oxophilicity comparable to thorium. − However, in contrast to a plethora of publications (>3600) focusing on Zr-MOFs, only around 100 exist for their Th-based counterparts (Figure ).…”

Section: Introductionmentioning

confidence: 99%

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

Lim,

Park,

Thaggard

et al. 2024

J. Am. Chem. Soc.

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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.

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Section: Introductionmentioning

confidence: 99%

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

Lim,

Park,

Thaggard

et al. 2024

J. Am. Chem. Soc.

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“…Rapidly expanding interest in areas like efficient nuclear stockpile recycling, development of effective nuclear fuel cycles, and preparation of isotopically pure radiological daughters for nuclear medicine has generated a rich scope of research surrounding actinide, including thorium (Th), chemistry. − At the same time, industrial demands in the energy and environmental sectors have brought solid-state actinide-based materials to the spotlight, with an emphasis on functional materials with high thermal and chemical stability. In this direction, metal–organic frameworks (MOFs) have recently attracted significant attention due to exceptional chemical, thermal, and mechanical stability, as well as structural integrity under γ radiation. − Design of Th-MOFs or any radioactive metal–organic compounds in general very often involves the use of nonradioactive surrogates as a first step, before transitioning to actinide-containing structures. Notably, employing nonradioactive surrogates is an important and accessible route toward studying actinides, and especially, transuranics, considering the additional licensing, advanced safety training, strict waste disposal, and even regulations limiting the quantity of radioactive compounds in a given laboratory.…”

Section: Introductionmentioning

confidence: 99%

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

Park,

Lim,

Thaggard

et al. 2024

J. Am. Chem. Soc.

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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.

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Switching from Molecules to Functional Materials: Breakthroughs in Photochromism With MOFs

Thaggard,

Kankanamalage,

Park

et al. 2024

Advanced Materials

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Photochromic materials with properties that can be dynamically tailored as a function of external stimuli are a rapidly expanding field driven by applications in areas ranging from molecular computing, nanotechnology, or photopharmacology to programable heterogeneous catalysis. Challenges arise, however, when translating the rapid, solution‐like response of stimuli‐responsive moieties to solid‐state materials due to the intermolecular interactions imposed through close molecular packing in bulk solids. As a result, the integration of photochromic compounds into synthetically programable porous matrices, such as metal‐organic frameworks (MOFs), has come to the forefront as an emerging strategy for photochromic material development. This review highlights how the core principles of reticular chemistry (on the example of MOFs) play a critical role in the photochromic material performance, surpassing the limitations previously observed in solution or solid state. The symbiotic relationship between photoresponsive compounds and porous frameworks with a focus on how reticular synthesis creates avenues toward tailorable photoisomerization kinetics, directional energy and charge transfer, switchable gas sorption, and synergistic chromophore communication is discussed. This review not only focuses on the recent cutting‐edge advancements in photochromic material development, but also highlights novel, vital‐to‐pursue pathways for multifaceted functional materials in the realms of energy, technology, and biomedicine.

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Kinetic Trapping of Photoluminescent Frameworks During High-Concentration Synthesis of Nonemissive Metal–Organic Frameworks

Cited by 5 publications

References 79 publications

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

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

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

Switching from Molecules to Functional Materials: Breakthroughs in Photochromism With MOFs

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