Backbone‐Directed Self‐Assembly of Interlocked Molecular Cyclic Metalla[3]Catenanes

Abstract

The efficient backbone‐directed self‐assembly of cyclic metalla[3]catenanes by the combination of tetrachloroperylenediimide (TCPDI)‐based dinuclear rhodium(III) clips and 4,4′‐diazopyridine or 4,4′‐dipyridylethylene ligands is realized in a single‐step strategy. The topology and coordination geometry of the cyclic metalla[3]catenanes are characterized by NMR spectroscopy, ESI‐TOF‐MS spectrometry, UV/Vis‐NIR spectroscopy, and X‐ray diffraction studies. The most remarkable feature of the formed cyclic metalla[3]catenane is that it contains π‐aggregates (ca. 2.6 nm) incorporating six TCPDIs. Further studies revealed that cyclic metalla[3]catenanes can be converted reversibly to their corresponding sodium adducts and precursor building blocks, respectively. This strategy opens the possibility of generating unique supramolecular structures from discrete functional π‐aggregates with precise arrangements.

Robust Fluorescent Self-Assembly System for Sensing of Phosgene, Thionyl Chloride, and Oxalyl Chloride

“…The concept of supramolecular self-assembly is a versatile method that can be exploited in the fields of bioimaging, , materials, sensors, oriented synthesis, − and drug delivery . Supramolecular self-assembly can proceed under the synergistic action of weak and reversible noncovalent interactions, such as hydrogen bonds, π–π stacking, van der Waals’ force, electrostatic interaction, and hydrophobicity effect. − According to the weakness and reversibility of noncovalent interactions, supramolecular self-assembly systems exhibit outstanding responses toward external stimuli, such as light, heat, electricity, magnetism, mechanical force, chemical substance, and biomolecules. − In other words, the self-assembly process can be finely adjusted by tuning the noncovalent interactions.…”