Gate-opening Induced by C8 Aromatics in a Double Diamondoid Coordination Network.

Coordination networks (CNs) that undergo guest-induced structural transformations are of topical interest thanks to their potential utility in separations and storage applications. Herein, we report a double diamondoid () topology CN, [Ni(bimpz)(bdc)(HO)] or (Hbdc = 1,4-benzenedicarboxylic acid, bimpz = 3,6-bis(imidazol-1-yl)pyridazine), that undergoes structural transformations induced by C8 isomers, i.e., xylenes (-xylene, OX; -xylene, MX; -xylene, PX) and ethylbenzene (EB). was characterized by single-crystal to single-crystal transformations from a nonporous phase, , to isostructural C8-loaded phases, namely and . accommodates two C8 isomers per Ni unit, resulting in relatively high uptake (ca. 50 wt %), but with low selectivity toward C8 isomers as found using nuclear magnetic resonance (NMR) and gas chromatography (GC). In addition, a narrow range of gate-opening pressures for each isomer was determined from dynamic vapor sorption, consistent with the nonadaptable nature of the C8-loaded phase determined crystallographically, also supported by modeling.