Mixing supramolecular gels based on enantiomers leads to re-arrangement of gel fibers at the molecular level, which results in more favorable packing and tunable properties. Bis(urea) compounds tagged with a phenylalanine methyl ester in racemic and enantiopure forms were synthesized. Both enantiopure and racemate compounds formed gels in a wide range of solvents and the racemate (1-rac) formed a stronger gel network compared with the enantiomers. The gel (1R+1S) obtained by mixing equimolar amount of enantiomers (1R and 1S) showed enhanced mechanical and thermal stability compared to enantiomers and racemate gels. The preservation of chirality in these compounds was analyzed by circular dichroism and optical rotation measurements. Analysis of the scanning electron microscopy (SEM) and atomic force microscopy (AFM) images revealed that the network in the mixed gel is a combination of enantiomers and racemate fibers, which was further supported by solid-state NMR. The analysis of the packing in xerogels by solid-state NMR spectra and the existence of twisted-tape morphology in SEM and AFM images confirmed the presence of both self-sorted and co-assembled fibers in mixed gel. The enhanced thermal and mechanical strength may be attributed to the enhanced intermolecular forces between the racemate and the enantiomer and the combination of both self-sorted and co-assembled enantiomers in the mixed gel.

The geometry and spatial orientation of the gelator molecules and the mode of various intermolecular non-covalent interactions are the key parameters, which dictate the structure and properties of low molecular...

The combination of strong coordination bonds and hydrogen bonding interactions were used to generate a series of supramolecular coordination materials (SCMs), which was achieved by reacting a bis-pyridyl amide ligand, namely N-(4-pyridyl)nicotinamide (4PNA) with copper(II), zinc(II), and cadmium(II) benzoates. The SCMs were structurally characterized using X-ray diffraction and the key intermolecular interactions were identified via Hirshfeld surface analysis. The role of solvent molecules on the supramolecular architecture was analyzed by synthesizing the SCMs in different solvents/solvent mixtures. A solvent-mediated solid-state structural transformation was observed in copper(II) SCMs and we were able to isolate the intermediate form of the crystal-to-crystal transformation process. The luminescence experiments revealed that complexation enhanced the fluorescence properties of 4PNA in the zinc(II) and cadmium(II) SCMs, but a reverse phenomenon was observed in the copper(II) SCMs. This work demonstrated the tuning of supramolecular assembly in coordination compounds as a function of solvents for generating SCMs with diverse properties.