Evolution from Octahedral to Icosahedral Metal-Organic Polyhedra Assembled by 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. The theoretical prediction shows that there are 6 possible polyhedra from (3,4)-c octahedron to (3,5)-c icosahedron with minimal transitivity (simplest possible). Except missing one 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 transitivitity principle and are well consistent with geometrical predictions.