{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,5,16]],"date-time":"2026-05-16T20:15:37Z","timestamp":1778962537867,"version":"3.51.4"},"reference-count":24,"publisher":"MDPI AG","issue":"8","license":[{"start":{"date-parts":[[2021,7,23]],"date-time":"2021-07-23T00:00:00Z","timestamp":1626998400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Symmetry"],"abstract":"<jats:p>Synthetic efforts targeting highly symmetrical metal\u2013organic frameworks (MOFs) have always been relentless, for the symmetry of a MOF\u2019s pore environment and overall crystal structure are relevant to the MOF\u2019s properties and behavior. Herein, we report a novel Th-based MOF constructed from assembling highly symmetrical Th-oxo clusters via in situ reductive coupling of nitroso groups on the cluster surface. Nitroso groups have long been known to dimerize in a reversible fashion. Putting them on the monovalent ligands that decorate the Th-oxo clusters can facilitate a downstream assembly process that link the said clusters in a controllable and predictable manner, preserving the overall symmetry in the MOF product. Moreover, the assembly can be made permanent by reducing the azodioxy moiety to azo, effectively locking the symmetrical MOF form. We believe this process of assembling pre-formed Th-oxo clusters helps the overall MOF adopt a highly symmetrical topology (face-centered cubic, fcu) resembling the well-known UiO series MOFs based on tetravalent Zr\/Hf.<\/jats:p>","DOI":"10.3390\/sym13081332","type":"journal-article","created":{"date-parts":[[2021,7,23]],"date-time":"2021-07-23T10:31:44Z","timestamp":1627036304000},"page":"1332","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["An fcu Th-MOF Constructed from In Situ Coupling of Monovalent Ligands"],"prefix":"10.3390","volume":"13","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-3292-7698","authenticated-orcid":false,"given":"Ting","family":"Song","sequence":"first","affiliation":[{"name":"School of Chemical Engineering, Sichuan University, Chengdu 610065, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7223-7934","authenticated-orcid":false,"given":"Wenlei","family":"Tang","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering, Sichuan University, Chengdu 610065, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Chuer","family":"Bao","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering, Sichuan University, Chengdu 610065, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Qiuxue","family":"Lai","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering, Sichuan University, Chengdu 610065, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1930-6224","authenticated-orcid":false,"given":"Zhiyuan","family":"Zhang","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering, Sichuan University, Chengdu 610065, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4756-970X","authenticated-orcid":false,"given":"Xuan","family":"Feng","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering, Sichuan University, Chengdu 610065, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9780-9062","authenticated-orcid":false,"given":"Chong","family":"Liu","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering, Sichuan University, Chengdu 610065, China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2021,7,23]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"3104","DOI":"10.1039\/C7CS90049J","article-title":"The new age of MOFs and of their porous-related solids","volume":"46","author":"Maurin","year":"2017","journal-title":"Chem. Soc. Rev."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"8037","DOI":"10.1021\/acs.chemrev.0c00836","article-title":"Introduction: Porous Framework Chemistry","volume":"120","author":"Long","year":"2020","journal-title":"Chem. Rev."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"1782","DOI":"10.1021\/ar800124u","article-title":"The Reticular Chemistry Structure Resource (RCSR) database of, and symbols for, crystal nets","volume":"41","author":"Peskov","year":"2008","journal-title":"Acc. Chem. Res."},{"key":"ref_4","unstructured":"(2021, June 15). According to the Cambridge Crystallographic Data Centre Statistics. Available online: https:\/\/www.ccdc.cam.ac.uk\/Community\/blog\/MOF-classification-search-screen\/."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"6643","DOI":"10.1002\/chem.201003211","article-title":"Modulated Synthesis of Zr-Based Metal-Organic Frameworks: From Nano to Single Crystals","volume":"17","author":"Schaate","year":"2011","journal-title":"Chem. A Eur. J."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"10307","DOI":"10.1002\/anie.201204475","article-title":"Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal-Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts","volume":"51","author":"Feng","year":"2012","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"6443","DOI":"10.1021\/ic300825s","article-title":"Synthesis, Structure, and Metalation of Two New Highly Porous Zirconium Metal\u2013Organic Frameworks","volume":"51","author":"Morris","year":"2012","journal-title":"Inorg. Chem."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"10294","DOI":"10.1021\/ja4050828","article-title":"Vapor-Phase Metalation by Atomic Layer Deposition in a Metal\u2013Organic Framework","volume":"135","author":"Mondloch","year":"2013","journal-title":"J. Am. Chem. Soc."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"7660","DOI":"10.1021\/ja401429x","article-title":"Tunable Rare-Earth fcu-MOFs: A Platform for Systematic Enhancement of CO2 Adsorption Energetics and Uptake","volume":"135","author":"Xue","year":"2013","journal-title":"J. Am. Chem. Soc."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"4330","DOI":"10.1021\/jacs.6b01233","article-title":"A Titanium\u2013Organic Framework as an Exemplar of Combining the Chemistry of Metal\u2013 and Covalent\u2013Organic Frameworks","volume":"138","author":"Nguyen","year":"2016","journal-title":"J. Am. Chem. Soc."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"156","DOI":"10.1016\/j.matt.2019.02.002","article-title":"Lattice Expansion and Contraction in Metal-Organic Frameworks by Sequential Linker Reinstallation","volume":"1","author":"Feng","year":"2019","journal-title":"Matter"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"2534","DOI":"10.1002\/anie.202012947","article-title":"An Imine-Linked Metal\u2013Organic Framework as a Reactive Oxygen Species Generator","volume":"60","author":"Li","year":"2021","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"11527","DOI":"10.1002\/anie.202002724","article-title":"Divergent Chemistry Paths for 3D and 1D Metallo-Covalent Organic Frameworks (COFs)","volume":"59","author":"Xu","year":"2020","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"830","DOI":"10.1038\/nchem.1730","article-title":"Constructing monocrystalline covalent organic networks by polymerization","volume":"5","author":"Beaudoin","year":"2013","journal-title":"Nat. Chem."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"48","DOI":"10.1126\/science.aat7679","article-title":"Single-crystal x-ray diffraction structures of covalent organic frameworks","volume":"361","author":"Ma","year":"2018","journal-title":"Science"},{"key":"ref_16","unstructured":"Edelstein, N.M., Fuger, J., and Morss, L.R. (2010). The Chemistry of the Actinide and Transactinide Elements, Springer. [5th ed.]."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"27","DOI":"10.1016\/j.ccr.2016.11.006","article-title":"Thorium coordination: A comprehensive review based on coordination number","volume":"333","author":"Tutson","year":"2017","journal-title":"Coord. Chem. Rev."},{"key":"ref_18","first-page":"1","article-title":"A mesoporous cationic thorium-organic framework that rapidly traps anionic persistent organic pollutants","volume":"8","author":"Li","year":"2017","journal-title":"Nat. Commun."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"14144","DOI":"10.1021\/jacs.8b07113","article-title":"Autoluminescent Metal-Organic Frameworks: Self-Photoemission of a Highly Stable Thorium MOF","volume":"140","author":"Andreo","year":"2018","journal-title":"J. Am. Chem. Soc."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"13299","DOI":"10.1021\/jacs.0c05272","article-title":"Unprecedented Radiation Resistant Thorium-Binaphthol MOF","volume":"142","author":"Gilson","year":"2020","journal-title":"J. Am. Chem. Soc."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"12765","DOI":"10.1002\/anie.201406852","article-title":"Conjugated-Protein Mimics with Molecularly Imprinted Reconstructible and Transformable Regions that are Assembled Using Space-Filling Prosthetic Groups","volume":"53","author":"Takeuchi","year":"2014","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_22","first-page":"2045","article-title":"Copper (I)\u2013Organic Frameworks for Catalysis: Networking Metal Clusters with Dynamic Covalent Chemistry","volume":"2","author":"Wei","year":"2020","journal-title":"CCS Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"6715","DOI":"10.1039\/D0CC02841J","article-title":"Modulated synthesis and isoreticular expansion of Th-MOFs with record high pore volume and surface area for iodine adsorption","volume":"56","author":"Li","year":"2020","journal-title":"Chem. Commun."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"2235","DOI":"10.1021\/ic502725y","article-title":"Thorium Terephthalates Coordination Polymers Synthesized in Solvothermal DMF\/H2O System","volume":"54","author":"Falaise","year":"2015","journal-title":"Inorg. Chem."}],"container-title":["Symmetry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-8994\/13\/8\/1332\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T06:34:00Z","timestamp":1760164440000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-8994\/13\/8\/1332"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,7,23]]},"references-count":24,"journal-issue":{"issue":"8","published-online":{"date-parts":[[2021,8]]}},"alternative-id":["sym13081332"],"URL":"https:\/\/doi.org\/10.3390\/sym13081332","relation":{},"ISSN":["2073-8994"],"issn-type":[{"value":"2073-8994","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,7,23]]}}}