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

The 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 en...

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Authors: Ruiz Bilbao, Estíbaliz, Iturrospe, Amaia, Reinoso, Santiago, Artetxe, Beñat, Beobide, Garikoitz, San Felices, Leire, Lezama, Luis, Gutiérrez Zorrilla, Juan M., Darwish, Shaza, Sensharma, Debobroto, Zaworotko, Michael J.
Format: article
Status:Published version
Publication Date:2023
Country:España
Institution:Universidad Pública de Navarra
Repository:Academica-e. Repositorio Institucional de la Universidad Pública de Navarra
OAI Identifier:oai:academica-e.unavarra.es:2454/46649
Online Access:https://hdl.handle.net/2454/46649
Access Level:Open access
Keyword:Microporous Materials
Polyoxometalates
Single-Crystal-to-Single-Crystal
Solid-State Isomerization
Water Sorption
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spelling Consecutive single-crystal-to-single-crystal isomerization of novel octamolybdate anions within a microporous hybrid framework with robust water sorption propertiesRuiz Bilbao, EstíbalizIturrospe, AmaiaReinoso, SantiagoArtetxe, BeñatBeobide, GarikoitzSan Felices, LeireLezama, LuisGutiérrez Zorrilla, Juan M.Darwish, ShazaSensharma, DebobrotoZaworotko, Michael J.Microporous MaterialsPolyoxometalatesSingle-Crystal-to-Single-CrystalSolid-State IsomerizationWater SorptionThe 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.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).WileyCienciasZientziakInstitute for Advanced Materials and Mathematics - INAMAT22023info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://hdl.handle.net/2454/46649reponame:Academica-e. Repositorio Institucional de la Universidad Pública de Navarrainstname:Universidad Pública de NavarraInglés© 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 madehttps://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:academica-e.unavarra.es:2454/466492026-06-17T12:41:47Z
dc.title.none.fl_str_mv Consecutive single-crystal-to-single-crystal isomerization of novel octamolybdate anions within a microporous hybrid framework with robust water sorption properties
title Consecutive single-crystal-to-single-crystal isomerization of novel octamolybdate anions within a microporous hybrid framework with robust water sorption properties
spellingShingle Consecutive single-crystal-to-single-crystal isomerization of novel octamolybdate anions within a microporous hybrid framework with robust water sorption properties
Ruiz Bilbao, Estíbaliz
Microporous Materials
Polyoxometalates
Single-Crystal-to-Single-Crystal
Solid-State Isomerization
Water Sorption
title_short Consecutive single-crystal-to-single-crystal isomerization of novel octamolybdate anions within a microporous hybrid framework with robust water sorption properties
title_full Consecutive single-crystal-to-single-crystal isomerization of novel octamolybdate anions within a microporous hybrid framework with robust water sorption properties
title_fullStr Consecutive single-crystal-to-single-crystal isomerization of novel octamolybdate anions within a microporous hybrid framework with robust water sorption properties
title_full_unstemmed Consecutive single-crystal-to-single-crystal isomerization of novel octamolybdate anions within a microporous hybrid framework with robust water sorption properties
title_sort Consecutive single-crystal-to-single-crystal isomerization of novel octamolybdate anions within a microporous hybrid framework with robust water sorption properties
dc.creator.none.fl_str_mv Ruiz Bilbao, Estíbaliz
Iturrospe, Amaia
Reinoso, Santiago
Artetxe, Beñat
Beobide, Garikoitz
San Felices, Leire
Lezama, Luis
Gutiérrez Zorrilla, Juan M.
Darwish, Shaza
Sensharma, Debobroto
Zaworotko, Michael J.
author Ruiz Bilbao, Estíbaliz
author_facet Ruiz Bilbao, Estíbaliz
Iturrospe, Amaia
Reinoso, Santiago
Artetxe, Beñat
Beobide, Garikoitz
San Felices, Leire
Lezama, Luis
Gutiérrez Zorrilla, Juan M.
Darwish, Shaza
Sensharma, Debobroto
Zaworotko, Michael J.
author_role author
author2 Iturrospe, Amaia
Reinoso, Santiago
Artetxe, Beñat
Beobide, Garikoitz
San Felices, Leire
Lezama, Luis
Gutiérrez Zorrilla, Juan M.
Darwish, Shaza
Sensharma, Debobroto
Zaworotko, Michael J.
author2_role author
author
author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ciencias
Zientziak
Institute for Advanced Materials and Mathematics - INAMAT2
dc.subject.none.fl_str_mv Microporous Materials
Polyoxometalates
Single-Crystal-to-Single-Crystal
Solid-State Isomerization
Water Sorption
topic Microporous Materials
Polyoxometalates
Single-Crystal-to-Single-Crystal
Solid-State Isomerization
Water Sorption
description The 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.
publishDate 2023
dc.date.none.fl_str_mv 2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2454/46649
url https://hdl.handle.net/2454/46649
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.rights.none.fl_str_mv https://creativecommons.org/licenses/by-nc-nd/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv reponame:Academica-e. Repositorio Institucional de la Universidad Pública de Navarra
instname:Universidad Pública de Navarra
instname_str Universidad Pública de Navarra
reponame_str Academica-e. Repositorio Institucional de la Universidad Pública de Navarra
collection Academica-e. Repositorio Institucional de la Universidad Pública de Navarra
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,812429

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