Addressed realization of multication complex arrangements in metal-organic frameworks.
The preparation of materials with structures composed of multiple metal cations that occupy specific sites is challenging owing to the difficulty of simultaneously addressing the incorporation of different elements at desired precise positions. We report how it is possible to use a metal-organic framework (MOF) built with a rod-shaped inorganic secondary building unit (SBU) to combine multiple metal elements at specific positions in a manner that is controllable at atomic and mesoscopic scales. Through the combination of four different metal elements at judiciously selected molar ratios, 20 MOFs of different compositions and the same topology have been prepared and characterized. The use of diffraction techniques, supported by density functional theory calculations, has led us to determine various possible atomic arrangements of the metal cations within the SBUs. In addition, seven of the compounds combine multiple types of atomic arrangements, which are mesoscopically distributed along the crystals. Given the large diversity and importance of rod-based MOFs, we believe that these findings offer a new general strategy to produce complex materials with required compositions and controllable arrangements of the metal cations for desired applications.