Electrochemically Mediated Syntheses of Titanium(III)-Based Metal-Organic Frameworks

Although metal-organic frameworks featuring coordinatively unsaturated transition metal sites are relatively common, examples with redox-active cations are rare. In this report, we describe the electrochemically mediated synthesis of Ti^III-MIL-101 from the inexpensive Ti⁴⁺ precursor TiCl₄. The framework obtained via electrosynthesis is identical to that prepared from the significantly more expensive and air-sensitive starting material TiCl₃. The above electrosynthetic strategy was also extended to prepare Ti^III-MIL-100 and two high-quality extended Ti^III-MIL structures, for the first time. These materials represent examples of titanium-based MOFs with extended pore structures. Several physical methods demonstrate that these materials are superior in quality to samples of the analogous MOFs prepared via conventional routes from starting exogenous TiCl₃. Given the ease with which the electrosyntheses may be carried out and their compatibility with a broad range of bridging ligands, we expect that this new methodology will find utility for the synthesis of a number of novel materials containing coordinatively unsaturated, redox-active metal cations.