Construction of Supramolecular Polymers with Different Topologies by Orthogonal Self-Assembly of Cryptand–Paraquat Recognition and Metal Coordination

Abstract

Recently, metal-coordinated orthogonal self-assembly has been used as a feasible and efficient method in the construction of polymeric materials, which can also provide supramolecular self-assembly complexes with different topologies. Herein, a cryptand with a rigid pyridyl group on the third arm derived from BMP32C10 was synthesized. Through coordination-driven self-assembly with a bidentate organoplatinum(II) acceptor or tetradentate Pd(BF4)2•4CH3CN, a di-cryptand complex and tetra-cryptand complex were prepared, respectively. Subsequently, through the addition of a di-paraquat guest, linear and cross-linked supramolecular polymers were constructed through orthogonal self-assembly, respectively. By comparing their proton nuclear magnetic resonance (1H NMR) and diffusion-ordered spectroscopy (DOSY) spectra, it was found that the degrees of polymerization were dependent not only on the concentrations of the monomers but also on the topologies of the supramolecular polymers.

Host–Guest Chemosensor Ensembles based on Water-Soluble Sulfonated Calix[n]arenes and a Pyranoflavylium Dye for the Optical Detection of Biogenic Amines

“…Supramolecular chemistry provides a wide range of receptor molecules, particularly macrocycles, that can be used as hosts in a variety of applications, garnering considerable interest from the scientific community. In terms of structural diversity, macrocycles, include cyclodextrins, , cucurbiturils, , crown ethers, cryptands, pillararenes, and calixarenes, , to give some examples. On the other hand, guest molecules are generally small molecules or ions that benefit from the host–guest interactions to improve their stability and bioavailability or even to tune their spectroscopic features, namely, colorimetric and fluorescent properties.…”

Stimuli-Responsive Macromolecular Self-Assembly

“…In 1981, Drexle et al introduced the assembly mode of living organisms into the discipline of chemistry, resulting in chemical self-assembly [2]. As the core of supramolecular chemistry, self-assembly is the spontaneous formation process of supramolecular structures or aggregates with specific structures and functions [3][4][5][6][7][8][9][10] through non-covalent bond interactions, such as van der Waals forces, hydrogen bonds, π-π interactions, electrostatic interaction, hydrophobic interaction, metal coordination bonds and other non-covalent bonding interactions [11][12][13]. The self-assembly process is driven by these non-covalent bond interactions, which can also maintain the stability and integrity of self-assembly structures.…”