A Tale of Two Trimers from Two Different Worlds: A COF‐Inspired Synthetic Strategy for Pore‐Space Partitioning of MOFs

Abstract

Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Unconventional Pyridyl Ligand Inclusion within a Flexible Metal‐Organic Framework Bearing an N,N′‐Diethylformamide (DEF)‐Solvated Cd5 Cluster Secondary Building Unit

“…We hoped to replace these seemingly weakly coordinating ligands with dipyridyls to partition the pore space. [8] Unexpectedly, this solid-state reaction did not proceed despite sufficient pore sizes of 1 a. Notably, we observed that pyridyl monomers could diffuse into the pores and, coordinated to the flanking Cd 2 + instead of replacing the seemingly weakly coordinated DEF solvates.…”

“…15.5 Å (20.3 Å-2 × CdÀ N bonds with 2.4 Å for each) would replace the two DEF solvates, thus partitioning the pore space. [8] To explore this possibility, we first reacted 1 a with dipyridyl ligands 4,4 ' -bipyridine (Bipy), 4,4 ' -azopyridine (Azopy), trans-1,2bis(4-pyridyl)ethylene (Bpee), and 4,4 ' -dipyridyl sulfide (Dps) in CHCl 3 . [3g,13] However, we found that no obvious substitution reaction occurred and the single-crystals slowly became opaque and then powered.…”

A Strategy for Constructing Pore‐Space‐Partitioned MOFs with High Uptake Capacity for C2 Hydrocarbons and CO2

“…In both first and second stages, we made use of the coordination assembly only. In the third stage which involves both covalent and coordination bond formation, we showed an example of using in situ formed organic molecule (through trimerization of pyridine‐4‐boronic acid) to direct the pacs formation …”

A Dual Threat: Redox‐Activity and Electronic Structures of Well‐Defined Donor–Acceptor Fulleretic Covalent‐Organic Materials

“…Merging the properties of three‐dimensional buckyballs (or buckybowls) and covalent‐organic frameworks (COFs) provides access to a novel class of materials combining ultrafast energy/electron transport characteristic of three‐dimensional (3D) fulleretic linkers with high modularity, crystallinity, and surface area, which are intrinsic properties of COFs . The precise donor–acceptor alignment achieved in the materials is imposed by the rigid COF scaffold and is crucial for efficient energy or charge transfer as it can influence the distance of exciton diffusion, π–π stacking, or Förster radius, and as a result, can enhance device performance …”