Consecutive single-crystal-to-single-crystal isomerization of novel octamolybdate anions within a microporous hybrid framework with robust water sorption properties
Fecha
2023Autor
Versión
Acceso abierto / Sarbide irekia
Tipo
Artículo / Artikulua
Versión
Versión publicada / Argitaratu den bertsioa
Impacto
|
10.1002/anie.202307436
Resumen
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 ...
[++]
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. [--]
Materias
Microporous Materials,
Polyoxometalates,
Single-Crystal-to-Single-Crystal,
Solid-State Isomerization,
Water Sorption
Editor
Wiley
Publicado en
Angewandte Chemie International 2023, 62, e202307436 (1 of 9)
Departamento
Universidad Pública de Navarra. Departamento de Ciencias /
Nafarroako Unibertsitate Publikoa. Zientziak Saila /
Universidad Pública de Navarra/Nafarroako Unibertsitate Publikoa. Institute for Advanced Materials and Mathematics - INAMAT2
Versión del editor
Entidades Financiadoras
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).
Aparece en las colecciones
Los documentos de Academica-e están protegidos por derechos de autor con todos los derechos reservados, a no ser que se indique lo contrario.
La licencia del ítem se describe como © 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 made