Programmed Pore Architectures in Modular Quaternary Metal–Organic Frameworks

Abstract

To generate metal-organic frameworks (MOFs) that are complex and modular yet well ordered, we present a strategy employing a family of three topologically distinct linkers that codes for the assembly of a highly porous quaternary MOF. By introducing substituted analogues of the ligands, a set of eight isoreticular frameworks is delivered, with the MOF structure systematically varied while the topology is maintained. To combat randomness and disorder, the substitution patterns of the ligands are designed to be compatible with their crystallographic site symmetries. MOFs produced in this way feature "programmed pores"--multiple functional groups compartmentalized in a predetermined array within a periodic lattice--and are capable of complex functional behavior. In these examples unconventional CO2 sorption trends, including capacity enhancements close to 100%, emerge from synergistic effects. Future PP-MOFs may be capable of enzyme-like heterogeneous catalysis and ultraselective adsorption.

Engineering Homochiral Metal–Organic Frameworks by Spatially Separating 1D Chiral Metal–Peptide Ladders: Tuning the Pore Size for Enantioselective Adsorption

“…[2] One of the most effective ways to control the pore size in MOFs is by rational connection of pre-designed, rigid building units (0D clusters,1 Dc hains, or 2D layers)t hrough organic linkers. [3] This approach, known as reticular synthesis, judiciously uses increasingly long linkers to expand pre-existing MOF structures by separating their characteristic building units. [4] It can thus provide as eries of isoreticular MOFs with larger pores.…”

Tritopic Triazatruxene Ligands for Multicomponent Metal‐Organic Frameworks

“…This may be useful for the detection of proton acceptors by luminescence quenching. Benefitting from the straightforward derivatization of H 3 tat, new ligands containing further substituents with different electronic and steric properties can be prepared to tune MOF features such as catalytic activity, gas adsorption and fluorescence output in a programmable way …”

Enhancing Multicomponent Metal–Organic Frameworks for Low Pressure Liquid Organic Hydrogen Carrier Separations

“…MUF‐7 (MUF=Massey University Framework) was the first member of this series. MUF‐7 exhibits an ith‐d topology, with pores that can be tuned in shape and chemical functionality by introducing functional groups to the linkers . Replacing the btb linker with a more rigid, truxene centered linker that retains the same metrics, such as 5,5′,10,10′,15,15′‐hexamethyltruxene‐2,7,12‐tricarboxylic acid (H 3 hmtt), produces MOFs that are particularly stable and easily prepared and derivatised .…”