Polymorphic Coordination Networks Responsive to CO2, Moisture, and Thermal Stimuli: Porous Cobalt(II) and Zinc(II) Fluoropyrimidinolates

Abstract The novel porous [{M(F‐pymo) 2 } n ] ⋅ 2.5 n H 2 O coordination networks (M=Co, Zn; F‐pymo=5‐fluoropyrimidin‐2‐olate), possessing sodalitic topology, have been synthesised and structurally characterised by means of powder diffraction methods. Thermodiffractometry demonstrated their plasticity: when heated up to 363 K, they reversibly transform into three‐dimensional dehydrated [{M(F‐pymo) 2 } n ] species, with significantly different lattice parameters. Further heating induces irreversible polymorphic transformations into layered phases, in which the original MN 4 coordination sphere changes into an MN 3 O one. A mixed‐metal phase, [{Co x Zn 1− x (F‐pymo) 2 } n ] ⋅ 2.5 n H 2 O, was also prepared, showing that zinc is preferentially inserted, when starting from a Co/Zn reagent ratio of 1:1. The solid–gas adsorption properties of the anhydrous 3D frameworks have been explored towards N 2 , H 2 (77 K) and CH 4 , CO 2 (273 K). These results show that these materials permit the diffusion of CO 2 molecules only. Remarkably, the CO 2 adsorption process for the [{Co(F‐pymo) 2 } n ] network proceeds in two steps: the first step takes place at low pressures (<600 kPa) and the second one above a threshold pressure of 600 kPa. By contrast, the [{Zn(F‐pymo) 2 } n ] network only permits CO 2 diffusion by applying pressures above 900 kPa. This type of behaviour is typical of porous networks with gated channels. The high CO 2 selectivity of these systems over the rest of the essayed probe gases is explained in terms of flexibility and polarity of the porous network. Finally, the magnetic studies on the Co II systems reveal that the as synthesised [{Co(F‐pymo) 2 } n ] ⋅ 2.5 n H 2 O material behaves as an antiferromagnet with a T N of about 29 K. At variance, the [{Co(F‐pymo) 2 } n ] layered phase shows an unusually weak ferromagnetic ordering below 17 K, arising from a spin‐canting phenomenon.