Multivariate MOFs (MTV-MOFs) constructed from multiple
components
with atomistic precision hold the promise for many fascinating developments
in both fundamental sciences and applications. Sequential linker installation
can be an effective method to introduce different functional linkers
into an MOF that contains coordinatively unsaturated metal sites.
However, in many cases, these linkers must be installed according
to a specific sequence and the complete synthetic flexibility and
freedom is yet to be realized. Here, we rationally decreased the size
of the primary ligand used in NPF-300, a Zr-MOF withscutopology (NPF = Nebraska Porous Framework), and synthesized its
isostructure, NPF-320. NPF-320 exhibits optimized pocket sizes which
allow for the post-synthetic installation of three secondary linkers
in all six permuted sequences via both linker exchange and installation,
forming a final quinary MTV-MOF via single-crystal-to-single-crystal
transformation. With the functionalization of the linkers from the
quinary MOF system, one will be able to construct MTV-MOFs not only
with variable porosity but also with unprecedented complexity and
encoded synthetic sequence information. The utility of sequential
linker installation was further demonstrated by the construction of
a donor–acceptor pair-based energy transfer system.