Abstract
The reactions of three isomeric pyridinedicarboxylic acid linkers – 2,4‐, 2,6‐, and 3,5‐pyridinedicarboxylic acid – with various aluminum salts were investigated by high‐throughput solvothermal synthesis. Two coordination compounds were obtained from the symmetrical linkers (2,6‐ and 3,5‐pyridinedicarboxylic acid). The former is based on molecular Al–O dimers, similar to those reported in the coordination polymer CAU‐16. The latter forms a porous extended framework and is a member of the CAU‐10 family of compounds. Full characterization of both compounds is reported. Crystal structures were determined from high‐resolution synchrotron powder diffraction data. The number of guest water molecules determined crystallographically is in excellent agreement with the number found by thermogravimetric and elemental analyses. It was found that the CAU‐10 analogue undergoes a reversible, displacive phase transition from a non‐centrosymmetric to a centrosymmetric space group on loss of guest water molecules, due to guest‐framework interactions.
Highlights
The application of metal-organic frameworks (MOFs) as water sorbents for de-/humidification and water production applications has grown in popularity in recent years.[1,2,3] A precondition for such use is long term stability under operating conditions, which is usually investigated by repeated cycles of ad- and desorption under hydrothermal conditions.[4]
Whilst the water sorption properties of CAU-10-pydc have been reported previously,[12] we present a full structural characterization of the compound and report a new dimeric Al–O cluster compound, closely related to CAU-16
Synchrotron powder X-ray diffraction (SR-PXRD) data were indexed in the tetragonal space group I41/amd, which is adopted by other desolvated members of the CAU-10 family of compounds (e.g. CAU-10-CH3[10] and MIL-160;[13] see Supporting Information for details of systematic absences)
Summary
The application of metal-organic frameworks (MOFs) as water sorbents for de-/humidification and water production applications has grown in popularity in recent years.[1,2,3] A precondition for such use is long term stability under operating conditions, which is usually investigated by repeated cycles of ad- and desorption under hydrothermal conditions.[4]. For 2 only the crystal structure of the as-prepared compound is reported, since no guest molecules are present and dehydration results in a non-crystalline product. Synchrotron powder X-ray diffraction (SR-PXRD) data were indexed in the tetragonal space group I41/amd, which is adopted by other desolvated members of the CAU-10 family of compounds (e.g. CAU-10-CH3[10] and MIL-160;[13] see Supporting Information for details of systematic absences).
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