{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,5]],"date-time":"2026-08-05T02:24:42Z","timestamp":1785896682213,"version":"3.56.0"},"reference-count":52,"publisher":"Wiley","issue":"17","license":[{"start":{"date-parts":[[2023,2,15]],"date-time":"2023-02-15T00:00:00Z","timestamp":1676419200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100010785","name":"Canada First Research Excellence Fund","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100010785","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000038","name":"Natural Sciences and Engineering Research Council of Canada","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100000038","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2023,3,22]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The reliable self\u2010assembly of microporous metal\u2010phosphonate materials remains a longstanding challenge. This stems from, generally, more coordination modes for the functional group allowing more dense structures, and stronger bonding driving less crystalline products. Here, a novel orthogonalized aryl\u2010phosphonate linker, 1,3,5\u2010tris(4\u2019\u2010phosphono\u20102\u2019,6\u2019\u2010dimethylphenyl) benzene (H<jats:sub>6<\/jats:sub>L3) has been used to direct formation of open frameworks. The peripheral aryl rings of H<jats:sub>6<\/jats:sub>L3 are orthogonalized relative to the central aromatic ring giving a tri\u2010cleft conformation of the linker in which small aromatic molecules can readily associate. When coordinated to magnesium ions, a series of porous crystalline metal\u2010organic, and hydrogen\u2010bonded metal\u2010organic frameworks (MOFs, HMOFs) are formed (CALF\u201041 (Mg), HCALF\u201042 (Mg), \u201043 (Mg)). While most metal\u2010organic frameworks are tailored based on choice of metal and linker, here, the network structures are highly dependent on the inclusion and structure of the guest aromatic compounds. Larger guests, and a higher stoichiometry of metal, result in increased solvation of the metal ion, resulting in networks with connectivities increasingly involving hydrogen\u2010bonds rather than direct phosphonate coordination. Upon thermal activation and aromatic template removal, the materials exhibit surface areas ranging from 400\u2013600\u2005m<jats:sup>2<\/jats:sup>\/g. Self\u2010assembly in the absence of aromatic guests yields mixtures of phases, frequently co\u2010producing a dense 3\u2010fold interpenetrated structure (1). Interestingly, a series of both more porous (530\u2013900\u2005m<jats:sup>2<\/jats:sup>\/g), and more robust solids is formed by complexing with trivalent metal ions (Al, Ga, In) with aromatic guest; however, these are only attainable as microcrystalline powders. The polyprotic nature of phosphonate linkers enables structural analogy to the divalent analogues and these are identified as CALF\u201041 analogues. Finally, insights to the structural transformations during metal ion desolvation in this family are gained by considering a pair of structurally related Co materials, whose hydrogen\u2010bonded (HCALF\u201044 (Co)) and desolvated (CALF\u201044 (Co)) coordination bonded networks were fully structurally characterized.<\/jats:p>","DOI":"10.1002\/chem.202203835","type":"journal-article","created":{"date-parts":[[2022,12,29]],"date-time":"2022-12-29T22:08:56Z","timestamp":1672351736000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":15,"title":["Microporous Metal\u2010Phosphonates with a Novel Orthogonalized Linker and Complementary Guests: Insights for Trivalent Metal Complexes from Divalent Metal Complexes"],"prefix":"10.1002","volume":"29","author":[{"given":"Martin","family":"Glavinovi\u0107","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Calgary  2500 University Drive NW Calgary AB T2N 1N4 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Justin H.","family":"Perras","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Calgary  2500 University Drive NW Calgary AB T2N 1N4 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Benjamin S.","family":"Gelfand","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Calgary  2500 University Drive NW Calgary AB T2N 1N4 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jian\u2010Bin","family":"Lin","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Calgary  2500 University Drive NW Calgary AB T2N 1N4 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Denis M.","family":"Spasyuk","sequence":"additional","affiliation":[{"name":"Canadian Light Source Inc. University of Saskatchewan  44 Innovation Boulevard Saskatoon SK S7N 2V3 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wen","family":"Zhou","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Calgary  2500 University Drive NW Calgary AB T2N 1N4 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3697-9890","authenticated-orcid":false,"given":"George K. H.","family":"Shimizu","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Calgary  2500 University Drive NW Calgary AB T2N 1N4 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,2,15]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7CS90049J"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201503835"},{"key":"e_1_2_8_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201503835"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja512973b"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1116275"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja3055639"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CS00688A"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/3527605746.ch15"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jssc.2005.07.003"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CS00075G"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CS00127C"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2019.04.003"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0DT01879A"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9CS00813F"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo901465f"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200902816"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/cg200074z"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/cm010681c"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/cm020987z"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja980793d"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2018.02.004"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja076094v"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201911861"},{"key":"e_1_2_8_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201911861"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr2002257"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2018.05.002"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemmater.9b01742"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.3390\/cryst9050270"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201901291"},{"key":"e_1_2_8_28_1","first-page":"1","volume":"13","author":"Ramesha B. M.","year":"2020","journal-title":"Materials (Basel)"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00107"},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202001917"},{"key":"e_1_2_8_31_1","doi-asserted-by":"publisher","DOI":"10.1002\/adom.202200213"},{"key":"e_1_2_8_32_1","doi-asserted-by":"publisher","DOI":"10.1039\/b802423p"},{"key":"e_1_2_8_33_1","doi-asserted-by":"publisher","DOI":"10.1021\/cm5044045"},{"key":"e_1_2_8_34_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cej.2016.05.061"},{"key":"e_1_2_8_35_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7TA07034A"},{"key":"e_1_2_8_36_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201600207"},{"key":"e_1_2_8_37_1","doi-asserted-by":"publisher","DOI":"10.1139\/v08-130"},{"key":"e_1_2_8_38_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201607745"},{"key":"e_1_2_8_38_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201607745"},{"key":"e_1_2_8_39_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CC01253D"},{"key":"e_1_2_8_40_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic801450m"},{"key":"e_1_2_8_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic400274e"},{"key":"e_1_2_8_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c10421"},{"key":"e_1_2_8_43_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4DT03698K"},{"key":"e_1_2_8_44_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202200874"},{"key":"e_1_2_8_45_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889802022112"},{"key":"e_1_2_8_46_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CC00681C"},{"key":"e_1_2_8_47_1","doi-asserted-by":"publisher","DOI":"10.1002\/aic.690110125"},{"key":"e_1_2_8_48_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cpc.2015.11.016"},{"key":"e_1_2_8_49_1","doi-asserted-by":"publisher","DOI":"10.1007\/s11814-017-0269-9"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202203835","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/chem.202203835","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202203835","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T18:41:50Z","timestamp":1760294510000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.202203835"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,2,15]]},"references-count":52,"journal-issue":{"issue":"17","published-print":{"date-parts":[[2023,3,22]]}},"alternative-id":["10.1002\/chem.202203835"],"URL":"https:\/\/doi.org\/10.1002\/chem.202203835","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,2,15]]},"assertion":[{"value":"2022-12-07","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2023-02-15","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202203835"}}