Control over Self-Assembly through Reversible Charging of the Aromatic Building Blocks in Photofunctional Supramolecular Fibers

Abstract

Self-assembling systems, whose structure and function can be reversibly controlled in situ are of primary importance for creating multifunctional supramolecular arrays and mimicking the complexity of natural systems. Herein we report on photofunctional fibers self-assembled from perylene diimide cromophores, in which interactions between aromatic monomers can be attenuated through their reduction to anionic species that causes fiber fission. Oxidation with air restores the fibers. The sequence represents reversible supramolecular depolymerization-polymerization in situ and is accompanied by a reversible switching of photofunction.

Hydrophobic Self‐Assembly Affords Robust Noncovalent Polymer Isomers

“…[7] Remarkably, 1 G and 1 P demonstrate dissimilar potentiodynamic characteristics. The CV and DPV of 1 G display two redox potentials at À0.78 and À0.57 V vs. SCE, and appear as broad peaks in DPV, whereas 1 P exhibits a very different pattern-a sharp peak at À0.62 V vs SCE (Figure 4 B).…”

“…The analogue of 1 having shorter PEG chains (PEG17) is not soluble in water, and shows self-assembly behavior (in water/THF mixtures) different from that of 1. [7] The compound 1 is readily dissolved in water to form a green solution (the green-colored assemblies are designated as 1 G, and can be converted into the purple-brown assemblies 1 P; see below). UV/vis spectra of 1 G exhibit significant red shifts and absorption-band broadening in comparison to disaggregated 1 (Figure 1).…”

Modular supramolecular ureidopyrimidinone polymer carriers for intracellular delivery

“…This concept has previously been employed to control growth and size of supramolecular polymers. 23 Next, zeta potential measurements showed positive values of 35.3 mV and 40.7 mV for a 50% and a fully cationic polymer respectively, while 2.57 mV was measured for the neutral polymer (Fig. 2d).…”

Coordination‐Driven Self‐Assembly of PEO‐Functionalized Perylene Bisimides: Supramolecular Diversity from a Limited Set of Molecular Building Blocks

“…A particularly instructive example was recently reported by Rybtchinski and co-workers, who investigated the selfassembly of poly(ethylene oxide)-substituted perylene bisimide derivatives, some of which were equipped with terpyridine ligands for the coordination of transition metals. [4] In their investigations, the authors combined amphiphilicity, polymer attachment, p-p stacking, and metallo-supramolecular interactions to prepare optoelectronically active organic materials with different supramolecular morphologies from essentially the same simple set of molecular building blocks.…”