Abstract
The solvothermal reaction of Cu 2ZrCl 6 and ZrCl 4 in benzene is shown to yield the molecular species ((bz) 2Cu) 2Zr 2Cl 10 · bz ( 1), which is characterized by single crystal X-ray diffraction. The structure consists of edge-shared dimers of zirconium chloride octahedra whose axial chlorides are bridged by bis-benzene chlorocuprate fragments. The Cu 2Zr 2 tetramers are linked in the crystal lattice by edge-to-face π-stacking of the coordinated and lattice benzene molecules, as well as benzene-to-chloride hydrogen bonding. Benzene is lost from this material in a stepwise fashion resulting in what are described to be chain, ((bz)Cu) 2Zr 2Cl 10 ( 2) and layered clay-type materials, Cu 2Zr 2Cl 10 ( 3). The desolvated materials, 2 and 3, reversibly sorb ethylene, as characterized by sorption isotherms, in situ pressure-resolved synchrotron X-ray diffraction and UV/Vis diffuse reflectance spectroscopy.
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