From Octahedral to Icosahedral Metal–Organic Polyhedra Assembled from Two Types of Polyoxovanadate Clusters

Design and synthesis of metal–organic polyhedra (MOPs) with targeted geometries from predetermined secondary building units (SBUs) is a long‐standing challenge in chemistry and material science. Theoretical prediction shows that there are 6 possible polyhedra from the 3‐coordinated, 4‐coordinated octahedron ((3,4)‐c octahedron) to (3,5)‐c icosahedron with minimal transitivity (simplest possible). Except for one missing polyhedron (mtr) due to the unfavorable angles, we report five MOPs based on these structures, including an octahedral (3,4)‐c VMOP‐21 (rdo), an icosahedral (3,5)‐c VMOP‐25 (trc), and three intermediate derived trinodal (3,4,5)‐c VMOP‐22–24 (ghm, hmg, xum). Remarkably, all these MOPs obey the minimal transitivity principle and are consistent with geometrical predictions. Get the MOP: The concept of reticular chemistry is used for the design of metal–organic polyhedra (MOPs) leading to a sequence of theoretically expected and experimentally characterized 3‐coordinated, 4‐coordinated and 5‐coordinated MOPs based on polyoxovanadate building blocks that all obey the minimal transitivity (simplest possible) principle.