Metalation Triggers Single Crystalline Order in a Porous Solid

We report the dramatic triggering of structural order in a Zr(IV)-based metal-organic framework (MOF) through docking of HgCl₂ guests. Although as-made crystals were unsuitable for single crystal X-ray diffraction (SCXRD), with diffraction limited to low angles well below atomic resolution due to intrinsic structural disorder, permeation of HgCl₂ not only leaves the crystals intact but also resulted in fully resolved backbone as well as thioether side groups. The crystal structure revealed elaborate HgCl₂-thioether aggregates nested within the host octahedra to form a hierarchical, multifunctional net. The chelating thioether groups also promote Hg(II) removal from water, while the trapped Hg(II) can be easily extricated by 2-mercaptoethanol to reactivate the MOF sorbent.