Hydrogen‐Bonded Organic Frameworks Based on Endless‐Stacked Amides for Iodine Capture and Detection

Abstract

Recently, hydrogen‐bonded organic frameworks (HOFs) have emerged as a rapidly advancing class of porous materials with significant potential for applications in the absorption and detection of various chemicals. Here, the unique ability of amide groups to form endless‐stacking H‐bonds is implemented in the design of HOFs. Starting from benzene‐1,3,5‐tricarboxamide and amide‐containing tribenzocyclynes as foundational building blocks, a diverse range of HOFs featuring 1D, 2D, or 3D hydrogen‐bonded frameworks has been synthesized. Among those, all three porous HOFs, HOF_B‐Hex, HOF_T‐Pr and HOF_T‐Hex exhibited permanent porosity, thereby demonstrating the effectiveness of amide‐based HOFs strategy. Notably, HOF_T‐Hex stands out with a 42% pore volume and an impressive iodine capture efficiency of 6.4 g g−1. The iodine capture capacity is influenced not only by pore volume but also by the presence of accessible π‐electrons within the material (i.e., electrons not engaged in a π–π stacking interaction. Furthermore, some of these HOFs exhibited fluorescent responses to iodine positioning them as highly promising materials for both the capture and sensing of iodine.

Monoatomic Nickel Wires via Columnar Self-Assembly of Tribenzocyclyne Nickel Complexes

“…In order to implement this approach, we have capitalized on the tendency of amide groups to lead to 1D columnar architectures. − For example, a series of benzene-1,3,5-tricarboxamides can be stacked in a face-to-face columnar arrangement where the amide H-bonds are sufficiently robust to counterbalance the electrostatic repulsions between the π-clouds of the stacked phenyl groups . In our case, the amide-derived H-bond would not only act as a directing group for the self-assembly of the nanowire but would also further stabilize the nanowire, in particular against Peierls instabilities.…”