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

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journal contribution
posted on 2023-09-11, 14:57 authored by Estibaliz Ruiz-Bilbao, Amaia Iturrospe, Santiago Reinoso, Beñat Artetxe, Garikoitz Beobide, Leire San Felices, Luis Lezama, Juan M. Gutiérrez-Zorrilla, Shaza DarwishShaza Darwish, DEBOBROTO SENSHARMADEBOBROTO SENSHARMA, MICHAEL ZAWOROTKOMICHAEL ZAWOROTKO

The 3D hybrid framework [{Cu(cyclam)}3(k-Mo8O27)]· 14H2O (1) (cyclam=1,4,8,11-tetraazacyclotetradecane) undergoes sequential single-crystal-to-single-crystal 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 3a 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.



Angewandte Chemie International Edition, 2023, e202307436


Wiley and Sons Ltd

Other Funding information

Funded by Eusko Jaurlaritza/Gobierno Vasco (EJ/GV, grants IT1722-22 and KK-2022/00045). E.R.B. thanks EJ/GV for her doctoral fellowship (PRE_2018_1_0143). Technical and human support from SGIker (UPV/EHU) is gratefully acknowledged.

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