Exploration of Chemically Cross-Linked Metal–Organic Frameworks

A series
of geometrically constrained, cross-linked benzene dicarboxylic
acid (bdc) derivatives have been synthesized and incorporated into
the canonical isoreticular metal–organic framework (IRMOF)
lattice. Only certain cross-links, which allow for the proper relative
orientation of the bdc subunits, form the desired IRMOF. Design criteria
from these cross-linked ligands allowed for the rational design of
two oligomeric ligands composed of three bdc monomers tethered together.
These oligomeric ligands were also readily incorporated into an IRMOF
lattice with a high degree of crystallinity and porosity, providing
a new dimension to rational ligand design for metal–organic
frameworks.