{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,9]],"date-time":"2026-10-09T20:03:36Z","timestamp":1791576216266,"version":"4.3.4"},"reference-count":54,"publisher":"Wiley","issue":"12","license":[{"start":{"date-parts":[[2024,10,12]],"date-time":"2024-10-12T00:00:00Z","timestamp":1728691200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001671","name":"European Synchrotron Radiation Facility","doi-asserted-by":"publisher","award":["CH\u20106220"],"award-info":[{"award-number":["CH\u20106220"]}],"id":[{"id":"10.13039\/501100001671","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Small Science"],"published-print":{"date-parts":[[2024,12]]},"abstract":"<jats:p>\n                    Due to their similar boiling points, separation of benzene and cyclohexane mixtures is among the current challenging processes faced by the petrochemical industry. As recently assessed, the soft imine\u2010based covalent organic framework [(TAM)(BDA)\n                    <jats:sub>2<\/jats:sub>\n                    ] (COF\u2010300; TAM\u2009=\u2009tetrakis(4\u2010aminophenyl)methane, BDA\u2009=\u2009terephthaldehyde) possesses higher affinity for benzene than cyclohexane in both static conditions at 298\u2009K and dynamic conditions in the range of 298\u2013348\u2009K. As shown in this contribution, in situ powder X\u2010ray diffraction while dosing benzene and cyclohexane vapors in the range of 0.01\u20134.74\u2009bar on the narrow\u2010pore form of COF\u2010300 confirmed the coherent switchability of its framework, unveiling the progressive formation of different intermediate\u2010 and large\u2010pore forms. In addition, a basket of otherwise inaccessible key crystallochemical details\u2014\u201con\/off\u201d structural\u2010feature changes cooperating to adsorption, primary adsorption sites, and host\u2013guest and guest\u2013guest interactions\u2014was successfully retrieved. Overall, these findings allowed to shed light on the framework dynamics underneath the previously observed selectivity toward benzene over cyclohexane, completing this case of study and providing relevant information for the design of new\u2010generation adsorbents for this applicative context.\n                  <\/jats:p>","DOI":"10.1002\/smsc.202400277","type":"journal-article","created":{"date-parts":[[2024,10,12]],"date-time":"2024-10-12T06:39:27Z","timestamp":1728715167000},"source":"Crossref","is-referenced-by-count":6,"title":["Investigating the Dynamics of a Soft Crystalline Covalent Organic Framework during Benzene and Cyclohexane Adsorption by in\u2009situ Powder X\u2010ray Diffraction"],"prefix":"10.1002","volume":"4","author":[{"ORCID":"https:\/\/orcid.org\/0009-0003-4146-1970","authenticated-orcid":false,"given":"Anna","family":"Mauri","sequence":"first","affiliation":[{"name":"Dipartimento di Scienza e Alta Tecnologia Universit\u00e0 degli Studi dell\u2019Insubria  Via Valleggio 9 22100 Como Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9474-7671","authenticated-orcid":false,"given":"Rebecca","family":"Vismara","sequence":"additional","affiliation":[{"name":"Dipartimento di Scienza e Alta Tecnologia Universit\u00e0 degli Studi dell\u2019Insubria  Via Valleggio 9 22100 Como Italy"},{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica Universidad de Granada  Avenida Fuentenueva S\/N 18071 Granada Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6167-3792","authenticated-orcid":false,"given":"Marco","family":"Moroni","sequence":"additional","affiliation":[{"name":"Dipartimento di Scienza e Alta Tecnologia Universit\u00e0 degli Studi dell\u2019Insubria  Via Valleggio 9 22100 Como Italy"},{"name":"Dipartimento di Chimica Universit\u00e0 degli Studi di Pavia  Via Taramelli 12 27100 Pavia Italy"},{"name":"Consorzio Interuniversitario Nazionale per la Scienza e la Tecnologia dei Materiali  Via Giusti 9 50121 Firenze Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7297-7759","authenticated-orcid":false,"given":"Esther","family":"Rold\u00e1n\u2010Molina","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica Universidad de Granada  Avenida Fuentenueva S\/N 18071 Granada Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8359-0397","authenticated-orcid":false,"given":"Jorge A. R.","family":"Navarro","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Inorg\u00e1nica Universidad de Granada  Avenida Fuentenueva S\/N 18071 Granada Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0335-5707","authenticated-orcid":false,"given":"Simona","family":"Galli","sequence":"additional","affiliation":[{"name":"Dipartimento di Scienza e Alta Tecnologia Universit\u00e0 degli Studi dell\u2019Insubria  Via Valleggio 9 22100 Como Italy"},{"name":"Consorzio Interuniversitario Nazionale per la Scienza e la Tecnologia dei Materiali  Via Giusti 9 50121 Firenze Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,10,12]]},"reference":[{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2QI00977C"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2020.213583"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.infocus.7e4004"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527821099"},{"key":"e_1_2_9_6_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-030-47340-2"},{"key":"e_1_2_9_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.9b00550"},{"key":"e_1_2_9_8_1","doi-asserted-by":"publisher","DOI":"10.1038\/natrevmats.2016.68"},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35072F"},{"key":"e_1_2_9_10_1","doi-asserted-by":"publisher","DOI":"10.1002\/adfm.201907847"},{"key":"e_1_2_9_11_1","first-page":"404","volume":"70","author":"Carrington E. J.","year":"2014","journal-title":"Acta Crystallogr."},{"key":"e_1_2_9_12_1","doi-asserted-by":"publisher","DOI":"10.17344\/acsi.2016.2610"},{"key":"e_1_2_9_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7TA04501H"},{"key":"e_1_2_9_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201802240"},{"key":"e_1_2_9_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202209907"},{"key":"e_1_2_9_16_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2018.04.018"},{"key":"e_1_2_9_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202004535"},{"key":"e_1_2_9_18_1","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.444"},{"key":"e_1_2_9_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b01097"},{"key":"e_1_2_9_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c12505"},{"key":"e_1_2_9_21_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-022-35674-8"},{"key":"e_1_2_9_22_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41563-023-01523-2"},{"key":"e_1_2_9_23_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CS00049C"},{"key":"e_1_2_9_24_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1139915"},{"key":"e_1_2_9_25_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CS00878F"},{"key":"e_1_2_9_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja8096256"},{"key":"e_1_2_9_27_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.aat7679"},{"key":"e_1_2_9_28_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CC09571J"},{"key":"e_1_2_9_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b13691"},{"key":"e_1_2_9_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.2c09911"},{"key":"e_1_2_9_31_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0376-7388(99)00337-3"},{"key":"e_1_2_9_32_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889813000629"},{"key":"e_1_2_9_33_1","first-page":"681","volume":"107","author":"Antoine C.","year":"1888","journal-title":"C.R Seances Acad. Sci."},{"key":"e_1_2_9_34_1","unstructured":"http:\/\/ddbonline.ddbst.com\/AntoineCalculation\/AntoineCalculationCGI.exe(accessed: September\u00a02024)."},{"key":"e_1_2_9_35_1","unstructured":"For benzene in the absence of pertinent information we assumed at a first approximation that the reported values could be applied also in the temperature range 256\u2013275 K."},{"key":"e_1_2_9_36_1","doi-asserted-by":"publisher","DOI":"10.1016\/0025-5408(88)90019-0"},{"key":"e_1_2_9_37_1","unstructured":"As explained in the Experimental Section to grant a better signal\u2010to\u2010noise ratio we acquired six scans for each pressure\/temperature value with the intention of summing them up; nonetheless in some cases the system evolved from one scan to the following one so that for the whole powder pattern refinements single scans or sums of two or three scans were used leading to a lower signal\u2010to\u2010noise ratio which discouraged further treatment."},{"key":"e_1_2_9_38_1","unstructured":"The unit cell volume of NP2 varies at a higher pace than that of NP1 (Figure 3) this justifying the observed coalescence atPBEN\u2009=\u20090.09 bar."},{"key":"e_1_2_9_39_1","doi-asserted-by":"publisher","DOI":"10.1038\/nature17430"},{"key":"e_1_2_9_40_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-019-11565-3"},{"key":"e_1_2_9_41_1","unstructured":"The unit cell volume value retrieved at 256 K during benzene dosage is lower than that calculated during the HR\u2010VT\u2010PXRD experiment probably because the degree of hydration increased due to water adsorption by COF\u2010300 from air humidity."},{"key":"e_1_2_9_42_1","doi-asserted-by":"publisher","DOI":"10.1107\/S002188980000248X"},{"key":"e_1_2_9_43_1","volume-title":"IUCr Monograph","author":"Young R. A.","year":"1981"},{"key":"e_1_2_9_44_1","unstructured":"The empty volume was estimated with the software Mercury (v. 2024.1.0 Cambridge Crystallographic Data Centre Cambridge United Kingdom) moving a probe of radius 1.2 \u00c5 along a grid of pace 0.2 \u00c5 after removing the guests occupying the 1D channels."},{"key":"e_1_2_9_45_1","doi-asserted-by":"publisher","DOI":"10.1107\/S1600576722004988"},{"key":"e_1_2_9_46_1","unstructured":"Clearly the amount of benzene adsorbed during the HR\u2010NA\u2010PXRD dosage does not match that of the volumetric adsorption isotherm at 298 K as the conditions of the two experiments are not comparable. As a representative example atPBEN\u2009=\u20090.76 bar (T\u2009=\u2009344 K) we retrieved 2.5 mol of benzene per f.u. to be compared to the value of 6.1 mol per f.u. extracted from the volumetric adsorption isotherm atPBEN\u2009=\u20090.81 bar (T\u2009=\u2009298 K)."},{"key":"e_1_2_9_47_1","unstructured":"For the HR\u2010NA\u2010PXRD data acquired atPBEN\u2009=\u20094.74 bar a particularly low value for the site occupation factor of benzene was found: this can be reasonably due to the small amount of amorphous phase characterizing this value of adsorbate pressure (see caption to Figure 2) since crystallinity loss may affect the total pore volume available for adsorption."},{"key":"e_1_2_9_48_1","unstructured":"We started at higher pressures than in the case of benzene given the persistence of NP as the major form up toPBEN\u2009=\u20090.19 bar."},{"key":"e_1_2_9_49_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jhazmat.2012.09.024"},{"key":"e_1_2_9_50_1","unstructured":"TOPAS\u2010R v. 3.0 Bruker AXS GmbH Karlsruhe Germany2005."},{"key":"e_1_2_9_51_1","volume-title":"Insight into benzene vs cyclohexane adsorption by the covalent organic framework COF\u2010300: The role of host\u2010guest interactions","author":"Mauri A."},{"key":"e_1_2_9_52_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889891010804"},{"key":"e_1_2_9_53_1","doi-asserted-by":"publisher","DOI":"10.1107\/S0021889898006001"},{"key":"e_1_2_9_54_1","unstructured":"To build up the rigid body modelling the independent portion of the framework the following bond distances and angles were adopted: endocyclic C\uf8ffC 1.40\u2009\u00c5; exocyclic C\uf8ffC and single C\uf8ffN 1.45\u2009\u00c5 or 1.50\u2009\u00c5; double C\uf8feN 1.30\u2009\u00c5; C\uf8ffH 0.95 \u00c5; bond angles 120\u00b0."},{"key":"e_1_2_9_55_1","unstructured":"To build up the rigid body modelling benzene the following bond distances and angles were adopted: C\uf8ffC 1.39\u2009\u00c5; C\uf8ffH 0.95\u2009\u00c5; angles 120\u00b0. To build up the rigid body modelling cyclohexane the chair conformation was adopted using the following bond distances and angles: C\uf8ffC 1.54\u2009\u00c5; C\uf8ffH 0.95\u2009\u00c5; angles 109.5\u00b0."}],"container-title":["Small Science"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/smsc.202400277","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,12,1]],"date-time":"2024-12-01T08:34:34Z","timestamp":1733042074000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/smsc.202400277"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,10,12]]},"references-count":54,"journal-issue":{"issue":"12","published-print":{"date-parts":[[2024,12]]}},"alternative-id":["10.1002\/smsc.202400277"],"URL":"https:\/\/doi.org\/10.1002\/smsc.202400277","archive":["Portico"],"relation":{},"ISSN":["2688-4046","2688-4046"],"issn-type":[{"value":"2688-4046","type":"print"},{"value":"2688-4046","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,10,12]]},"article-number":"2400277"}}