A Metal-Organic Framework Incorporating Eight Different Size Rare-Earth Metal Elements: Toward Multifunctionality A La Carte

Multi-metallic multivariate (MTV) rare earth (RE) metal-organic frameworks (MOFs) are of interest for the development of multifunctional materials, however examples with more than three RE cations are rare and obstructed by compositional segregation during synthesis. Herein, this work demonstrates the synthesis of a multi-metallic MTV RE MOF incorporating two, four, six, or eight different RE ions with different sizes and in nearly equimolar amounts and no compositional segregation. The MOFs are formed by a combination of RE cations (La, Ce, Eu, Gd, Tb, Dy, Y, and Yb) and a 1,7-di(4-carboxyphenyl)-1,7-dicarba-closo-dodecaborane (mCB-L) linker. The steric bulkiness and acidity of mCB-L is crucial for the incorporation of different size RE ions into the MOF structure. Demonstration of the incorporation of all RE cations is performed via compositional and structural characterization. The more complex MTV MOF, including all eight RE ions (mCB-8RE), are also characterized using optical, thermal, and magnetic techniques. Element-selective X-ray absorption spectroscopy and X-ray Magnetic Circular Dichroism measurements allow us to characterize spectroscopically each of the eight RE ions and determine their magnetic moments. This work paves the way for the investigation of MTV MOFs with the possibility to combine RE ions a la carte for diverse applications.