Controlled Formation of a Main Chain Supramolecular Polymer Based on Metal-Ligand Interactions and a Thiol-Ene Click Reaction.

Supramolecular polymers with multiple functionalities and hierarchical structures have received considerable attention and become a hot research topic over the past years. Herein, a main-chain supramolecular polymer has been successfully fabricated by using metal-ligand interactions and a thiol-ene click reaction. 1 H NMR, UV/Vis, DOSY, and viscosity measurements were carried out to investigate the molecular recognition and the process of supramolecular polymerization. From the study, the orthogonality between thiol-ene click reactions and the terpyridine-metal ions complexation behavior was testified, and supramolecular polymeric assemblies could be constructed by a one pot method. In the meantime, due to the incorporation of metal-ligand interactions, the supramolecular polymer shows stimuli-responsive properties toward chemical stimuli. Hence, this work could provide a methodology for developing supramolecular polymers as smart materials.

Metallo-supramolecular polymers derived from benzothiadiazole-based platinum acetylide complexes for fluorescent security application.

Metallo-supramolecular polymers with the incorporation of benzothiadiazole-substituted organoplatinum moiety have been successfully constructed. The designed monomer displays intense fluorescence signals, which are severely quenched upon the supramolecular polymerization process. On-off switching of fluorescence can be further exploited for data security materials in response to the chemical stimuli. Accordingly, the resulting supramolecular polymers can be regarded as a novel and efficient candidate toward information processing applications.

Construction of supramolecular hyperbranched polymers via the "tweezering directed self-assembly" strategy.

A bis-alkynylplatinum(II) terpyridine tweezer-alkynylgold(III) diphenylpyridine guest is shown to maintain the specific complexation in the presence of a B21C7-secondary ammonium salt recognition motif, which facilitates the formation of supramolecular hyperbranched polymers via the "tweezering directed self-assembly" strategy.

Cooperative complexation of amino acid derivatives to platinum acetylide-based bolaamphiphile.

A platinum(II) acetylide-based bolaamphiphile equipped with two peripheral B18C6 moieties has been successfully prepared, which demonstrates cooperative recognition behavior toward l-alanine ester salt in chloroform. In a polar methanol/chloroform (3/1, v/v) medium, the amino acid additives influence the aggregation of the bolaamphiphile significantly, leading to the morphological transition from nanospherical to disordered structures. The adaptive properties of the current host-guest binary system will benefit the development of stimuli-responsive supramolecular materials.

Responsive supramolecular polymers based on the bis[alkynylplatinum(II)] terpyridine molecular tweezer/arene recognition motif.

Supramolecular polymers are constructed based on the novel bis[alkynylplatinum(II)] terpyridine molecular tweezer/pyrene recognition motif. Successive addition of anthracene as the diene and cyano-functionalized dienophile triggers the reversible supramolecular polymerization process, thus advancing the concept of utilizing Diels-Alder chemistry to access stimuli-responsive materials in compartmentalized systems.

Main-chain supramolecular polymers based on orthogonal benzo-21-crown-7/secondary ammonium salt and terpyridine/metal ion recognition motifs.

Orthogonal self-assembly of multiple components represents an efficient strategy to afford hierarchical and multifunctional assemblies. Here, we demonstrate the orthogonal recognition behaviors between benzo-21-crown-7/secondary ammonium salt and terpyridine/metal ions (Fe(2+) or Zn(2+) ) recognition motifs. Main-chain supramolecular polymers are subsequently achieved via "one-pot" mixing of the three monomers together (heteroditopic monomer 1, homoditopic secondary ammonium salt monomer 2, and Fe(BF4 )2 •6H2 O or Zn(OTf)2 ), which are confirmed by (1) H NMR, UV-Vis, DOSY, and viscosity measurements. Moreover, different metal ions (Fe(2+) or Zn(2+) ) exert considerable effects on the size of the resulting supramolecular polymers. Integration of two different types of non-covalent interactions renders dynamic and responsive properties for the resulting supramolecular polymers, as triggered by a variety of external stimuli such as temperature, potassium cation, as well as stronger chelating ligands. Therefore, the current work is a prerequisite for the future application of such orthogonal assemblies as intelligent supramolecular materials.

Formation of stimuli-responsive supramolecular polymeric assemblies via orthogonal metal-ligand and host-guest interactions.

Linear supramolecular polymers, assembled via the combination of orthogonal terpyridine-Zn(2+) and benzo-21-crown-7/secondary ammonium salt recognition motifs, exhibit dynamic properties responsive to various external stimuli.