Consecutive single-crystal-to-single-crystal isomerization of novel octamolybdate anions within a microporous hybrid framework with robust water sorption properties

Ruiz Bilbao, EstíbalizIturrospe, AmaiaReinoso, SantiagoArtetxe, BeñatBeobide, GarikoitzSan Felices, LeireLezama, LuisGutiérrez Zorrilla, Juan M.Darwish, ShazaSensharma, DebobrotoZaworotko, Michael J.2023-10-262023-10-262023Ruiz‐Bilbao, E., Iturrospe, A., Reinoso, S., Artetxe, B., Beobide, G., San Felices, L., Lezama, L., Gutiérrez‐Zorrilla, J. M., Darwish, S., Sensharma, D., & Zaworotko, M. J. (2023). Consecutive single‐crystal‐to‐single‐crystal isomerization of novel octamolybdate anions within a microporous hybrid framework with robust water sorption properties. Angewandte Chemie International Edition, 62(42), e202307436. https://doi.org/10.1002/anie.2023074361433-785110.1002/anie.202307436https://academica-e.unavarra.es/handle/2454/46649The 3D hybrid framework [{Cu(cyclam)}3(kMo8O27)]· 14H2O (1) (cyclam=1,4,8,11-tetraazacyclotetradecane) undergoes sequential single-crystal-to-singlecrystal transformations upon heating to afford two different anhydrous phases (2 a and 3a). These transitions modify the framework dimensionality and enable the isomerization of k-octamolybdate (k-Mo8) anions into λ (2 a) and μ (3 a) forms through metal migration. Hydration of 3 a involves condensation of one water molecule to the cluster to afford the γ-Mo8 isomer in 4, which dehydrates back into 3a through the 6a intermediate. In contrast, 2a reversibly hydrates to form 5, exhibiting the same Mo8 cluster as that of 1. It is remarkable that three of the Mo8 clusters (k, λ and μ) are new and that up to three different microporous phases can be isolated from 1 (2 a, 3a, and 6a). Water vapor sorption analyses show high recyclability and the highest uptake values for POM-based systems. The isotherms display an abrupt step at low humidity level desirable for humidity control devices or water harvesting in drylands.application/pdfeng© 2023 The Authors. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are madeMicroporous MaterialsPolyoxometalatesSingle-Crystal-to-Single-CrystalSolid-State IsomerizationWater SorptionConsecutive single-crystal-to-single-crystal isomerization of novel octamolybdate anions within a microporous hybrid framework with robust water sorption propertiesinfo:eu-repo/semantics/article2023-10-26info:eu-repo/semantics/openAccess