2026-04-14T02:10:44Zhttps://recercat.cat/oai/request

oai:recercat.cat:2072/4777722024-11-04T08:33:46Zcom_2072_98col_2072_378192

Modulation of the Dynamics of a Two-Dimensional Interweaving Metal-Organic Framework through Induced Hydrogen Bonding Fernández-Seriñán, Pilar Roztocki, K. Safarifard, Vahid Guillerm, Vincent Rodríguez-Hermida, Sabina Juanhuix, Judith Imaz, Inhar Morsali, Ali Maspoch Comamala, Daniel Benzenedicarboxylate Dynamic materials External stimulus Isostructural Meta positions Metalorganic frameworks (MOFs) Pore phase Pyridyl Two-dimensional Zinc metal Inducing, understanding, and controlling the flexibility in metal-organic frameworks (MOFs) are of utmost interest due to the potential applications of dynamic materials in gas-related technologies. Herein, we report the synthesis of two isostructural two-dimensional (2D) interweaving zinc(II) MOFs, TMU-27 [Zn(bpipa)(bdc)] and TMU-27-NH [Zn(bpipa)(NH-bdc)], based on N,N'-bis-4-pyridyl-isophthalamide (bpipa) and 1,4-benzenedicarboxylate (bdc) or 2-amino-1,4-benzenedicarboxylate (NH-bdc), respectively. These frameworks differ only by the substitution at the meta-position of their respective bdc groups: an H atom in TMU-27 vs an NH group in TMU-27-NH. This difference strongly influences their respective responses to external stimuli, since we observed that the structure of TMU-27 changed due to desolvation and adsorption, whereas TMU-27-NH remained rigid. Using single-crystal X-ray diffraction and CO-sorption measurements, we discovered that upon CO sorption, TMU-27 undergoes a transition from a closed-pore phase to an open-pore phase. In contrast, we attributed the rigidification in TMU-27-NH to intermolecular hydrogen bonding between interweaving layers, namely, between the H atoms from the bdc-amino groups and the O atoms from the bpipa-amide groups within these layers. Additionally, by using scanning electron microscopy to monitor the CO adsorption and desorption in TMU-27, we were able to establish a correlation between the crystal size of this MOF and its transformation pressure. 2024 Article https://ddd.uab.cat/record/301377 urn:10.1021/acs.inorgchem.3c04522 urn:oai:ddd.uab.cat:301377 urn:icn2uab:6608480 urn:scopus_id:85187992370 urn:articleid:1520510Xv63n12p5552 urn:pmid:38484385 urn:pmc-uid:10966731 urn:pmcid:PMC10966731 urn:oai:pubmedcentral.nih.gov:10966731 urn:oai:egreta.uab.cat:publications/5fc4eb46-7a1c-47e4-90dc-4401da02e951 http://hdl.handle.net/2072/477772 eng European Commission 101019003 Agencia Estatal de Investigación PID2021-124804NB-I00 Agència de Gestió d'Ajuts Universitaris i de Recerca 2021/SGR-00458 Agencia Estatal de Investigación CEX2021-001214-S Inorganic chemistry ; Vol. 63, Issue 12 (March 2024), p. 5552-5558 open access Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original. https://creativecommons.org/licenses/by/4.0/ application/pdf