Reversible Switching between Nonporous and Porous Phases of a New SIFSIX Coordination Network Induced by a Flexible Linker Ligand

Closed-to-open structural transformations in flexible coordination networks are of potential utility in gas storage and separation. Herein, we report the first example of a flexible SiF₆^2--pillared square grid material, [Cu(SiF₆)(L)₂]_n (L = 1,4-bis(1-imidazolyl)benzene), SIFSIX-23-Cu. SIFSIX-23-Cu exhibits reversible switching between nonporous (β1) and several porous (α, Î1, Î2, and Î3) phases triggered by exposure to N₂, CO₂, or H₂O. In addition, heating β1 to 433 K resulted in irreversible transformation to a closed polymorph, β2. Single-crystal X-ray diffraction studies revealed that the phase transformations are enabled by rotation and geometrical contortion of L. Density functional theory calculations indicated that L exhibits a low barrier to rotation (as low as 8 kJmol^-1) and a rather flat energy surface. In situ neutron powder diffraction studies provided further insight into these sorbate-induced phase changes. SIFSIX-23-Cu combines stability in water for over a year, high CO₂ uptake (ca. 216 cm³/g at 195 K), and good thermal stability.