Unraveling the Arrangement of Al and Fe within the Framework Explains the Magnetism of Mixed-Metal MIL-100(Al,Fe)

[Image: see text] Properties of mixed-metal MOFs depend on the distribution of different metals within their frameworks. Determination of this distribution is often very challenging. Using an example of aluminum- and iron-containing MIL-100, we demonstrate that (27)Al NMR spectroscopy, when combined with first-principles calculations and magnetic, X-band electron paramagnetic resonance, Fe K-edge extended X-ray absorption fine structure, and Mössbauer measurements, enables one to accurately determine the arrangement of Al and Fe within the metal trimers, which are the basic building units of MIL-100. In this particular material, the incorporation of Fe and Al on the framework metal sites is random. Crucial for deciphering the arrangement is detecting NMR signals, shifted because of the strong hyperfine interaction between the (27)Al nuclei and the unpaired electronic spins of Fe(3+) ions, assigning the shifted signals aided by first-principles calculations of hyperfine couplings, and quantitatively evaluating the NMR intensities and the measured effective magnetic moment.