To access structomers with level 3 intermixing, conditions are required in which the interactions between adjacent cages are effectively disrupted while dative bonds between PWs in a monometallic cage are faithfully retained. RhCu-kofo-3 and MoCu-kofo-3 were prepared by dissolving the intact single-metal cages and permitting them to intermix in solution before kofo-3 was crystallized out via addition of an appropriate anti-solvent. RhCu-kofo-4 and MoCu-kofo-4 were prepared by mechanochemistry. Mild grinding of dry monometallic MOPs powders separated monometallic aggregates along grain boundaries so that appreciable single metal ensembles are observed in kofo-4 structures (Fig. ). If desired, the MOP structomers can also be converted into multi-component MOFs via the insertion of a second ligand L2 in a specific lattice position. To ensure that the spatial distribution of metal centers set up in the MOP was faithfully inherited by the MOF, we extended the single crystal transformation of Cu24(BDC-OH)24 reported by Choe and Kwak for dabco (dabco = 1,4-diazabicyclo[2.2.2]octane) to a range of different L2 ligands and multi-metallic MOPs . With an optimized procedure in hand, we could show that Cu24(L1)24 with L1 = BDC-t Bu or BDC-OH proved equally effective, copper 20 substitution by Rh, Mo or Pd is readily tolerated, and L2 linkers carrying a range of functional groups such as diazo, amide or urea could be incorporated (Fig. and Supplementary Figs. 42-51). The recovery of soluble Cu24 MOPs from a MOF structure was also extended from L2 = bipy (bipy = 4,4′-bipyridine), which was previously achieved via ligand displacement with pyridine , to encompass more strongly coordinating L2 ligands via an acid-catalyzed selective ligand removal strategy (Supplementary Fig. ). Facile MOP -MOF interconversion ensures that structomers can be accessed not only for MOPs, an important class of materials in their own right , but an entire suite of distinct MOF structures that can be generated by the insertion of structurally or functionally distinct L2 ligands.