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

Lim, Jaewoong; Park, Kyoung Chul; Thaggard, Grace C.; Liu, Yuan; Maldeni Kankanamalage, Buddhima K. P.; Toler, Donald J.; Ta, An T.; Kittikhunnatham, Preecha; Smith, Mark D.; Phillpot, Simon R.; Shustova, Natalia B.

doi:10.1021/jacs.4c02327

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

Journal Article · 22 April 2024 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.4c02327 · OSTI ID:2429711

Lim, Jaewoong ^[1]; Park, Kyoung Chul ^[2]; Thaggard, Grace C. ^[2]; Liu, Yuan ^[3]; Maldeni Kankanamalage, Buddhima K. P. ^[2]; Toler, Donald J. ^[2]; Ta, An T. ^[3]; Kittikhunnatham, Preecha ^[4]; Smith, Mark D. ^[2];

^[3];

^[2]

University of South Carolina, Columbia, SC (United States); University of South Carolina
University of South Carolina, Columbia, SC (United States)
University of Florida, Gainesville, FL (United States)
Chulalongkorn University, Bangkok (Thailand)

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. Altogether, 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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Research Organization:: University of South Carolina, Columbia, SC (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation (NSF)

Grant/Contract Number:: SC0016574

OSTI ID:: 2429711

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 17 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (64)

Detection of Radioactive Gas with Scintillating MOFs Mauree, Sharvanee; Villemot, Vincent; Hamel, Matthieu Advanced Functional Materials, Vol. 33, Issue 31 https://doi.org/10.1002/adfm.202302877	journal	April 2023
Metal–Organic Frameworks Based on Group 3 and 4 Metals Feng, Liang; Pang, Jiandong; She, Ping Advanced Materials, Vol. 32, Issue 44 https://doi.org/10.1002/adma.202004414	journal	September 2020
Smart Tetraphenylethene‐Based Luminescent Metal–Organic Frameworks with Amide‐Assisted Thermofluorochromics and Piezofluorochromics Zhu, Zhong‐Hong; Bi, Changjiang; Zou, Hua‐Hong Advanced Science, Vol. 9, Issue 16 https://doi.org/10.1002/advs.202200850	journal	March 2022
Photochromic Metal-Organic Frameworks: Reversible Control of Singlet Oxygen Generation Park, Jihye; Feng, Dawei; Yuan, Shuai Angewandte Chemie International Edition, Vol. 54, Issue 2 https://doi.org/10.1002/anie.201408862	journal	December 2014
Flexible Zirconium Metal-Organic Frameworks as Bioinspired Switchable Catalysts Yuan, Shuai; Zou, Lanfang; Li, Haixia Angewandte Chemie International Edition, Vol. 55, Issue 36 https://doi.org/10.1002/anie.201604313	journal	June 2016
High Uptake of ReO ₄ ⁻ and CO ₂ Conversion by a Radiation-Resistant Thorium-Nickle [Th ₄₈ Ni ₆ ] Nanocage-Based Metal-Organic Framework Xu, Hang; Cao, Chun-Shuai; Hu, Han-Shi Angewandte Chemie International Edition, Vol. 58, Issue 18 https://doi.org/10.1002/anie.201901786	journal	March 2019
Heterometallic Actinide‐Containing Photoresponsive Metal‐Organic Frameworks: Dynamic and Static Tuning of Electronic Properties Martin, Corey R.; Leith, Gabrielle A.; Kittikhunnatham, Preecha Angewandte Chemie International Edition, Vol. 60, Issue 15 https://doi.org/10.1002/anie.202016826	journal	February 2021
Selective Crystallization of Rare‐Earth Ions into Cationic Metal‐Organic Frameworks for Rare‐Earth Separation Yang, Huajun; Peng, Fang; Schier, Danielle E. Angewandte Chemie International Edition, Vol. 60, Issue 20 https://doi.org/10.1002/anie.202017042	journal	April 2021
High Water Adsorption MOFs with Optimized Pore‐Nanospaces for Autonomous Indoor Humidity Control and Pollutants Removal Zhu, Neng‐Xiu; Wei, Zhang‐Wen; Chen, Cheng‐Xia Angewandte Chemie International Edition, Vol. 61, Issue 4 https://doi.org/10.1002/anie.202112097	journal	December 2021
Monte Carlo Simulation‐Guided Design of a Thorium‐Based Metal–Organic Framework for Efficient Radiotherapy‐Radiodynamic Therapy Xu, Ziwan; Luo, Taokun; Mao, Jianming Angewandte Chemie International Edition, Vol. 61, Issue 46 https://doi.org/10.1002/anie.202208685	journal	October 2022
f‐block MOFs: A Pathway to Heterometallic Transuranics Park, Kyoung Chul; Kittikhunnatham, Preecha; Lim, Jaewoong Angewandte Chemie International Edition, Vol. 62, Issue 5 https://doi.org/10.1002/anie.202216349	journal	December 2022
High‐Porosity Metal‐Organic Framework Glasses Xu, Wentao; Hanikel, Nikita; Lomachenko, Kirill A. Angewandte Chemie International Edition, Vol. 62, Issue 16 https://doi.org/10.1002/anie.202300003	journal	March 2023
Unveiling the Unique Roles of Metal Coordination and Modulator in the Polymorphism Control of Metal‐Organic Frameworks Li, Zi‐Jian; Ju, Yu; Zhang, Zeya Chemistry – A European Journal, Vol. 27, Issue 70 https://doi.org/10.1002/chem.202103062	journal	November 2021
Dynamic properties of a flexible metal-organic framework exhibiting a unique “picture frame”-like crystal morphology Sumida, Kenji; Horike, Nao; Furukawa, Shuhei Nano Research, Vol. 14, Issue 2 https://doi.org/10.1007/s12274-020-3002-7	journal	August 2020
Fabrication of an efficient and sensitive colorimetric biosensor based on Uricase/ Th-MOF for uric acid sensing in biological samples Badoei-dalfard, Arastoo; Sohrabi, Nasrin; Karami, Zahra Biosensors and Bioelectronics, Vol. 141 https://doi.org/10.1016/j.bios.2019.111420	journal	September 2019
Functionalized Zr-UiO-67 metal-organic frameworks: Structural landscape and application Vahabi, Amir Hossein; Norouzi, Fataneh; Sheibani, Esmaeil Coordination Chemistry Reviews, Vol. 445 https://doi.org/10.1016/j.ccr.2021.214050	journal	October 2021
Advances of MOFs and COFs for photocatalytic CO2 reduction, H2 evolution and organic redox transformations Luo, Tian; Gilmanova, Leisan; Kaskel, Stefan Coordination Chemistry Reviews, Vol. 490 https://doi.org/10.1016/j.ccr.2023.215210	journal	September 2023
Superior chemical stability of UiO-66 metal-organic frameworks (MOFs) for selective dye adsorption Ahmadijokani, Farhad; Mohammadkhani, Rahman; Ahmadipouya, Salman Chemical Engineering Journal, Vol. 399 https://doi.org/10.1016/j.cej.2020.125346	journal	November 2020
Electronic structures and magnetism of Zr-, Th-, and U-based metal-organic frameworks (MOFs) by density functional theory Pandey, Shubham; Demaske, Brian; Ejegbavwo, Otega A. Computational Materials Science, Vol. 184 https://doi.org/10.1016/j.commatsci.2020.109903	journal	November 2020
New 1D chiral Zr-MOFs based on in situ imine linker formation as catalysts for asymmetric C C coupling reactions Nguyen, Khoa D.; Ehrling, Sebastian; Senkovska, Irena Journal of Catalysis, Vol. 386 https://doi.org/10.1016/j.jcat.2020.03.034	journal	June 2020
Adsorptive separation of xenon/krypton mixtures using a zirconium-based metal-organic framework with high hydrothermal and radioactive stabilities Lee, Seung-Joon; Yoon, Tae-Ung; Kim, Ah-Reum Journal of Hazardous Materials, Vol. 320 https://doi.org/10.1016/j.jhazmat.2016.08.057	journal	December 2016
Zirconium-Based Metal–Organic Frameworks as Reusable Antibacterial Peroxide Carriers for Protective Textiles Ma, Kaikai; Cheung, Yuk Ha; Xie, Haomiao Chemistry of Materials, Vol. 35, Issue 6 https://doi.org/10.1021/acs.chemmater.2c03288	journal	March 2023
Exploring the Role of Hexanuclear Clusters as Lewis Acidic Sites in Isostructural Metal–Organic Frameworks Lyu, Jiafei; Zhang, Xuan; Li, Peng Chemistry of Materials, Vol. 31, Issue 11 https://doi.org/10.1021/acs.chemmater.9b00960	journal	May 2019
Structural Features of Zirconium-Based Metal–Organic Frameworks Affecting Radiolytic Stability Hanna, Sylvia L.; Rademacher, David X.; Hanson, Donald J. Industrial & Engineering Chemistry Research, Vol. 59, Issue 16 https://doi.org/10.1021/acs.iecr.9b06820	journal	April 2020
Mechanochemistry as a Reconstruction Tool of Decomposed Metal–Organic Frameworks Lee, Hong Kyu; Lee, Jae Hwa; Moon, Hoi Ri Inorganic Chemistry, Vol. 60, Issue 16 https://doi.org/10.1021/acs.inorgchem.1c00610	journal	June 2021
Encapsulation of Polymetallic Oxygen Clusters in a Mesoporous/Microporous Thorium-Based Porphyrin Metal–Organic Framework for Enhanced Photocatalytic CO ₂ Reduction Huang, Zhi-Wei; Hu, Kong-Qiu; Mei, Lei Inorganic Chemistry, Vol. 61, Issue 8 https://doi.org/10.1021/acs.inorgchem.1c04033	journal	February 2022
Unveiling the Structure–Modulator Relationships in Thorium-Based Metal–Organic Framework Crystallization Hou, Shujing; Liu, Fusheng; Xie, Haomiao Inorganic Chemistry, Vol. 62, Issue 14 https://doi.org/10.1021/acs.inorgchem.2c04447	journal	March 2023
A Quantitative Scale of Oxophilicity and Thiophilicity Kepp, Kasper P. Inorganic Chemistry, Vol. 55, Issue 18 https://doi.org/10.1021/acs.inorgchem.6b01702	journal	August 2016
Stabilization of an Unprecedented Hexanuclear Secondary Building Unit in a Thorium-Based Metal–Organic Framework Li, Peng; Goswami, Subhadip; Otake, Ken-ichi Inorganic Chemistry, Vol. 58, Issue 6 https://doi.org/10.1021/acs.inorgchem.8b03511	journal	February 2019
Ultrastable Thorium Metal–Organic Frameworks for Efficient Iodine Adsorption Li, Zi-Jian; Yue, Zenghui; Ju, Yu Inorganic Chemistry, Vol. 59, Issue 7 https://doi.org/10.1021/acs.inorgchem.9b03602	journal	March 2020
Product Inhibition and the Catalytic Destruction of a Nerve Agent Simulant by Zirconium-Based Metal–Organic Frameworks Liao, Yijun; Sheridan, Thomas; Liu, Jian ACS Applied Materials & Interfaces, Vol. 13, Issue 26 https://doi.org/10.1021/acsami.1c05062	journal	June 2021
Effect of Missing-Linker Defects and Ion Exchange on Stability and Proton Conduction of a Sulfonated Layered Zr-MOF Szufla, Monika; Navarro, Jorge A. R.; Góra-Marek, Kinga ACS Applied Materials & Interfaces, Vol. 15, Issue 23 https://doi.org/10.1021/acsami.3c03873	journal	June 2023
Selectivity Regulation in Au-Catalyzed Nitroaromatic Hydrogenation by Anchoring Single-Site Metal Oxide Promoters Zhao, Ji-Xiao; Chen, Chao-Qiu; Xing, Cai-Hong ACS Catalysis, Vol. 10, Issue 4 https://doi.org/10.1021/acscatal.9b04855	journal	January 2020
Disclosing the Complex Structure of UiO-66 Metal Organic Framework: A Synergic Combination of Experiment and Theory Valenzano, Loredana; Civalleri, Bartolomeo; Chavan, Sachin Chemistry of Materials, Vol. 23, Issue 7, p. 1700-1718 https://doi.org/10.1021/cm1022882	journal	April 2011
Topology-Guided Design and Syntheses of Highly Stable Mesoporous Porphyrinic Zirconium Metal–Organic Frameworks with High Surface Area Liu, Tian-Fu; Feng, Dawei; Chen, Ying-Pin Journal of the American Chemical Society, Vol. 137, Issue 1 https://doi.org/10.1021/ja5111317	journal	December 2014
Sequential Linker Installation: Precise Placement of Functional Groups in Multivariate Metal–Organic Frameworks Yuan, Shuai; Lu, Weigang; Chen, Ying-Pin Journal of the American Chemical Society, Vol. 137, Issue 9 https://doi.org/10.1021/ja512762r	journal	March 2015
Crystallizing Atomic Xenon in a Flexible MOF to Probe and Understand Its Temperature-Dependent Breathing Behavior and Unusual Gas Adsorption Phenomenon Wang, Hao; Warren, Mark; Jagiello, Jacek Journal of the American Chemical Society, Vol. 142, Issue 47 https://doi.org/10.1021/jacs.0c09475	journal	November 2020
Ultrastable High-Connected Chromium Metal–Organic Frameworks Yang, Huajun; Peng, Fang; Hong, Anh N. Journal of the American Chemical Society, Vol. 143, Issue 36 https://doi.org/10.1021/jacs.1c07277	journal	August 2021
MOFs with 12-Coordinate 5f-Block Metal Centers Lv, Kai; Urbank, Christian; Patzschke, Michael Journal of the American Chemical Society, Vol. 144, Issue 7 https://doi.org/10.1021/jacs.1c13127	journal	February 2022
Imparting Functionality and Enhanced Surface Area to a 2D Electrically Conductive MOF via Macrocyclic Linker Pham, Hoai T. B.; Choi, Ji Yong; Huang, Shaofeng Journal of the American Chemical Society, Vol. 144, Issue 23 https://doi.org/10.1021/jacs.2c03793	journal	June 2022
Capture Instead of Release: Defect-Modulated Radionuclide Leaching Kinetics in Metal–Organic Frameworks Park, Kyoung Chul; Martin, Corey R.; Leith, Gabrielle A. Journal of the American Chemical Society, Vol. 144, Issue 35 https://doi.org/10.1021/jacs.2c06905	journal	August 2022
Chemical Vapor Deposition of Edge-on Oriented 2D Conductive Metal–Organic Framework Thin Films Choe, Myeonggeun; Koo, Jin Young; Park, Ina Journal of the American Chemical Society, Vol. 144, Issue 37 https://doi.org/10.1021/jacs.2c07135	journal	September 2022
Optimization of Pore-Space-Partitioned Metal–Organic Frameworks Using the Bioisosteric Concept Yang, Huajun; Chen, Yichong; Dang, Candy Journal of the American Chemical Society, Vol. 144, Issue 44 https://doi.org/10.1021/jacs.2c09349	journal	October 2022
Quantifying Ligand Binding to the Surface of Metal–Organic Frameworks Wang, Austin; Barcus, Kyle; Cohen, Seth M. Journal of the American Chemical Society, Vol. 145, Issue 30, p. 16821-16827 https://doi.org/10.1021/jacs.3c04892	journal	July 2023
Radiation-Induced De Novo Defects in Metal–Organic Frameworks Boost CO₂ Sorption Chen, Junchang; Zhang, Mingxing; Shu, Jie Journal of the American Chemical Society, Vol. 145, Issue 43 https://doi.org/10.1021/jacs.3c07778	journal	October 2023
Shaping the Water-Harvesting Behavior of Metal–Organic Frameworks Aided by Fine-Tuned GPT Models Zheng, Zhiling; Alawadhi, Ali H.; Chheda, Saumil Journal of the American Chemical Society, Vol. 145, Issue 51, p. 28284-28295 https://doi.org/10.1021/jacs.3c12086	journal	December 2023
New Heterometallic Zirconium Metalloporphyrin Frameworks and Their Heteroatom-Activated High-Surface-Area Carbon Derivatives Lin, Qipu; Bu, Xianhui; Kong, Aiguo Journal of the American Chemical Society, Vol. 137, Issue 6 https://doi.org/10.1021/jacs.5b00076	journal	February 2015
Ultraporous, Water Stable, and Breathing Zirconium-Based Metal–Organic Frameworks with ftw Topology Deria, Pravas; Gómez-Gualdrón, Diego A.; Bury, Wojciech Journal of the American Chemical Society, Vol. 137, Issue 40 https://doi.org/10.1021/jacs.5b08860	journal	September 2015
Multifaceted Modularity: A Key for Stepwise Building of Hierarchical Complexity in Actinide Metal–Organic Frameworks Dolgopolova, Ekaterina A.; Ejegbavwo, Otega A.; Martin, Corey R. Journal of the American Chemical Society, Vol. 139, Issue 46 https://doi.org/10.1021/jacs.7b09496	journal	November 2017
Autoluminescent Metal–Organic Frameworks (MOFs): Self-Photoemission of a Highly Stable Thorium MOF Andreo, Jacopo; Priola, Emanuele; Alberto, Gabriele Journal of the American Chemical Society, Vol. 140, Issue 43 https://doi.org/10.1021/jacs.8b07113	journal	October 2018
Ligand Rigidification for Enhancing the Stability of Metal–Organic Frameworks Lv, Xiu-Liang; Yuan, Shuai; Xie, Lin-Hua Journal of the American Chemical Society, Vol. 141, Issue 26 https://doi.org/10.1021/jacs.9b02947	journal	May 2019
Thermodynamics and Electronic Properties of Heterometallic Multinuclear Actinide-Containing Metal–Organic Frameworks with “Structural Memory” Ejegbavwo, Otega A.; Martin, Corey R.; Olorunfemi, Oyindamola A. Journal of the American Chemical Society, Vol. 141, Issue 29 https://doi.org/10.1021/jacs.9b04737	journal	June 2019
Sensing and capture of toxic and hazardous gases and vapors by metal–organic frameworks Wang, Hao; Lustig, William P.; Li, Jing Chemical Society Reviews, Vol. 47, Issue 13 https://doi.org/10.1039/C7CS00885F	journal	January 2018
Multiple functional groups in UiO-66 improve chemical warfare agent simulant degradation Kalaj, Mark; Palomba, Joseph M.; Bentz, Kyle C. Chemical Communications, Vol. 55, Issue 37 https://doi.org/10.1039/C9CC02252J	journal	January 2019
A mixed-ligand strategy regulates thorium-based MOFs Huang, Zhi-wei; Hu, Kong-qiu; Mei, Lei Dalton Transactions, Vol. 49, Issue 4 https://doi.org/10.1039/C9DT04158C	journal	January 2020
Unravelling a long-lived ligand-to-metal cluster charge transfer state in Ce–TCPP metal organic frameworks Yang, Sizhuo; Hu, Wenhui; Nyakuchena, James Chemical Communications, Vol. 56, Issue 90 https://doi.org/10.1039/D0CC04116E	journal	January 2020
Unravelling the true MOF-5 luminescence Villemot, Vincent; Hamel, Matthieu; Pansu, Robert B. RSC Advances, Vol. 10, Issue 31 https://doi.org/10.1039/D0RA02509G	journal	January 2020
Synthesis, characterization and application of defective metal–organic frameworks: current status and perspectives Xiang, Wenlong; Zhang, Yueping; Chen, Yifei Journal of Materials Chemistry A, Vol. 8, Issue 41 https://doi.org/10.1039/D0TA08009H	journal	January 2020
Structural resolution and mechanistic insight into hydrogen adsorption in flexible ZIF-7 Klein, Ryan A.; Shulda, Sarah; Parilla, Philip A. Chemical Science, Vol. 12, Issue 47 https://doi.org/10.1039/D1SC04618G	journal	January 2021
Multivariate zeolitic imidazolate frameworks with an inverting trend in flexibility Halder, Arijit; Klein, Ryan A.; Lively, Rachel Chemical Communications, Vol. 58, Issue 81 https://doi.org/10.1039/D2CC04362A	journal	January 2022
Recent advances in the applications of thorium-based metal–organic frameworks and molecular clusters Li, Zi-Jian; Guo, Xiaofeng; Qiu, Jie Dalton Transactions, Vol. 51, Issue 19 https://doi.org/10.1039/D2DT00265E	journal	January 2022
A facile synthesis of UiO-66, UiO-67 and their derivatives Katz, Michael J.; Brown, Zachary J.; Colón, Yamil J. Chemical Communications, Vol. 49, Issue 82 https://doi.org/10.1039/c3cc46105j	journal	January 2013
Solubility and Solubility-Limiting Solid Phase in M(IV)-OH-Dicarboxylate Ternary Aqueous System Kobayashi, Taishi; Sasaki, Takayuki; Takagi, Ikuji Journal of Nuclear Science and Technology, Vol. 48, Issue 7 https://doi.org/10.1080/18811248.2011.9711786	journal	July 2011
Handling fluorinated gases as solid reagents using metal-organic frameworks Keasler, Kaitlyn T.; Zick, Mary E.; Stacy, Emily E. Science, Vol. 381, Issue 6665 https://doi.org/10.1126/science.adg8835	journal	September 2023

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

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