Controlling the Length of Cooperative Supramolecular Polymers with Chain Cappers

Abstract

The design and the characterization of supramolecular additives to control the chain length of benzene-1,3,5-tricarboxamide (BTA) cooperative supramolecular polymers under thermodynamic equilibrium is unraveled. These additives act as chain capperso fs upramolecular polymers and feature one face as reactive as the BTAd iscotic to interact strongly with the polymere nd, whereas the other face is nonreactive and therefore impedes further polymerization. Such ad esign requires fine tuning of the conformational preorganization of the amides and the steric hindrance of the motif. The chain capperss tudied are monotopic derivatives of BTA, modified by partial N-methylation of the amides or by positioning of ab ulky cyclotriveratrylene cage on one face of the BTAu nit. This study not only clarifies the interplay between structural variations and supramolecular interactions, but it also highlights the necessity to combine orthogonal characterizationmethods, spectroscopy and light scattering, to elucidate the structures and compositions of supramolecular systems.

Recent progress and future challenges in the supramolecular polymerization of metal-containing monomers

“…We hypothesize that size restricted self-assembly can be an ideal addition towards LSP to control the nanoscale size regime. In this regard, distinct topologies, templated self-assembly 99 as well as the use of end-capping compounds 56,100,101 represent approaches that can enforce a definitive size limit. This potential has further been realized in detailed studies of particularly arranged and elongated oligomeric dye assemblies.…”

Control and Transfer of Chirality Within Well-Defined Tripodal Supramolecular Cages

“…Finally, the authors proposed, based on 1 H-NMR observations, that the transfer of chirality observed in the solid states might be retained in solution. Interestingly, this cage 7 , was used as the chain capper of BTA based supramolecular polymers allowing to control their length: whereas the external face of the BTA unit of 7 interacts with the polymer, the CTV unit crowds the other face, preventing further polymerization (ter Huurne et al, 2020 ).…”

Temperature-dependent modulation by biaryl-based monomers of the chain length and morphology of biphenyl-based supramolecular polymers

“…Porphyrins form a notable exception to this observation, since complexation of small ligands to metallated porphyrins only occurs on free monomers or on chain ends of the supramolecular polymer. [40][41][42][43][44] As a result, only a handful of chain cappers or sequestrators have been successfully designed [45][46][47][48][49][50] and the current lack of general principles to rationally designed comonomers in supramolecular polymers impedes further application of these functionally diverse materials.…”