| Abstract: | 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. |
