“Breathing” in Adsorbate‐Responsive Metal Tetraphosphonate Hybrid Materials

Breathe easy : Reversible H 2 O and NH 3 gas uptake by 2D calcium tetraphosphonates (see figure) is accompanied by framework structural changes similar to those previously reported for some carboxylate‐based hybrids. This breathing mechanism is accompanied by a volume increase of 55 %, while maintaining the topology and crystallinity of the material. magnified image The structures of various layered calcium tetraphosphonates (CaH 6 DTMP; H 8 DTMP=hexamethylenediamine tetrakis(methylenephosphonic acid)), have been determined. Starting from CaH 6 DTMP ⋅ 2H 2 O, thermal treatment and subsequent exposure to NH 3 and/or H 2 O vapors led to four new compounds that showed high storage capacity of guest species between the layers (up to ten H 2 O/NH 3 molecules) and a maximum volume increase of 55 %. The basic building block for these phosphonates consists of an eight‐membered ring chelating Ca 2+ through two phoshonate groups, and the organic ligand is located within the layers, which are held together by hydrogen bonds. The structural analysis revealed that the uptake/removal of guest species (H 2 O and NH 3 ) induces significant changes in the framework not only by changing the interlayer distances but also through important conformational changes of the organic ligand. An anisotropic breathing motion could be quantified by the changes of the unit‐cell dimensions and ligand arrangements in four crystalline derivatives. Complete characterization revealed the existence of interconversion reactions between the different phases upon gas uptake and release. The observed behavior represents, to the best of our knowledge, the first example of a breathing‐like mechanism in metal phosphonates that possess a 2D topology.