Modulating self-assembly and polymorph transitions in bisdendronized squaramides.

Supramolecular self-assembly is an advanced approach for constructing ordered nanoscale architectures with broad applications. While the principles of supramolecular polymerization have been thoroughly explored in artificial small molecules, polymer transformations remain barely explored, likely due to the lack of suitable reference models presenting well-defined and reversible transitions between aggregates. In this study, we introduce a series of bisdendronized squaramides (SQs) 1-3, showcasing complex self-assembly behaviours involving four distinct aggregates, three different interaction patterns, and various thermodynamically controlled polymorph transformations.

Reaction contest: hydrolysis intramolecular cyclisation reaction in alkyl squaramate esters.

The stability and hydrolytic behavior of squaramate esters in aqueous solutions have been investigated. The structure of squaramates and the nature of adjacent groups significantly influence their aqueous stability and reactivity towards nucleophiles. Squaramate esters, lacking or containing weakly basic neighboring group participation (NGP) substitutions, remain stable up to pH 9.

Light-Driven Photoconversion of Squaramides with Implications in Anion Transport.

Simple, clean and fast photoconversion of aniline-derived squaramides was achieved by flashlight illumination. UV irradiation enabled the photochemical squaramide ring-opening to generate 1,2-bisketenes, which DMSO trapped as the nucleophilic oxidant. The only photoproducts isolated were 3,4-arylamino maleic anhydrides, which present conformational preferences very different from those of their parent squaramides.

Thermoreversible Polymorph Transitions in Supramolecular Polymers of Hydrogen-Bonded Squaramides.

Hydrogen-bonded squaramide (SQ) supramolecular polymers exhibit uncommon thermoreversible polymorph transitions between particle- and fiber-like nanostructures. SQs 1-3, with different steric bulk, self-assemble in solution into particles (AggI) upon cooling to 298 K, and SQs 1 and 2, with only one dendronic group, show a reversible transformation into fibers (AggII) by further decreasing the temperature to 288 K. Nano-DSC and UV/Vis studies on SQ 1 reveal a concentration-dependent transition temperature and ΔH for the AggI-to-AggII conversion, while the kinetic studies on SQ 2 indicate the on-pathway nature of the polymorph transition.

Dual role of silver in a fluorogenic -squaraine probe based on Ag(I)-π interactions.

In the presence of Ag(i), the monoanion of cyano-N-squaraine (I) generates an intense fluorescence turn-on response. Experimental evidence and DFT calculations reveal a sequence of deprotonation-coordination events in which the Ag(i) ions play a dual role as a Lewis acid and coordinating metal. The observed effect is highly selective for Ag(i) compared to other metals.