Tunable Flexibility and Porosity of the Metal–Organic Framework DUT-49 through Postsynthetic Metal Exchange
Bikash Garai, Volodymyr Bon, Simon Krause, Friedrich Schwotzer, Martin Gerlach, Irena Senkovska, Stefan Kaskel
Abstract
. The single-crystal-to-single-crystal conversion allowed characterization of the new MOFs by single crystal X-ray diffraction, indicating identical structure and topology compared with that of previously explored DUT-49(Cu) framework. This approach is proven successful in achieving Mn-Mn and Cd-Cd dimers, which are rare examples of M-M paddle-wheel SBUs. The relative stability and flexibility of the resulted frameworks are observed to be highly sensitive to the metal ion of the framework, following the trends predicted by the Irving-Williams series. DUT-49(Ni) was recognized as a second material from the DUT-49 series showing adsorption-induced transitions. A sequential increase in framework flexibility from rigid to flexible and from flexible to NGA has been achieved through selective incorporation of metal centers into the structure. Finally, heterometallic structures are formed by selective and controlled exchange of metal ions to finely tune the flexibility and NGA phenomenon of the framework.