Phthalate mediated hydrogelation of a pyrene based system: a novel scaffold for shape-persistent, self-healing luminescent soft material

Abstract

Two-component super-hydrogelation triggered by the acid–base interaction of a L-histidine appended pyrenyl derivative (PyHis) and phthalic acid (PA) was reported. The use of isomeric isophthalic or terephthalic acid or other comparable acids in place of PA does not lead to salt formation and therefore hydrogelation is not observed. Excimer formation of the pyrenyl unit has not been detected although the PyHis : PA = 1 : 1 system undergoes extensive self-assembly in aqueous solution. The synergistic effect of intermolecular H-bonding forces, π–π stacking, electrostatic interactions, etc. is found to be responsible for robust hydrogel formation. Development of chiral supramolecular assemblies has been verified through circular dichroism spectroscopy. Morphological investigations involving the PyHis : PA = 1 : 1 system show vesicular nano-structures with a definite bilayer width at relatively low concentrations. The latter fuses to construct coiled-coil left-handed helical fibers upon increase in the concentrations of the gelators. The intertwining of the resultant helical fibers eventually results in hydrogel formation. The probable bilayer packing in the self-assembled structures has been probed using X-ray diffraction (XRD) studies and lanthanide sensitization, which suggests that the polar imidazolium hydrogen phthalate unit of the gelator forms the head group and faces the hydrophilic water environment while the hydrophobic pyrenyl units sit inside the hydrophobic core of the bilayer. The hydrogel exhibits multi-stimuli responsiveness including thixotropic behavior. In addition, shape-persistent as well as rapid self-healing behaviour of the hydrogel was established. Furthermore load-bearing characteristics of the hydrogel have also been demonstrated.