Synthesis and Self‐Assembly of Novel s‐Tetrazine‐Based Gelator

The design, synthesis and self‐assembly of new symmetrical 3,6‐bis(4‐(3,4,5‐tris(dodecyloxy)benzoate)phenyl)‐1,2,4,5‐tetrazine were described. The novel gelator, sym‐tetrazine, was prepared by addition reaction of 4‐cyanophenol with hydrazine monohydrate followed by oxidation reaction to afford the corresponding 3,6‐bis(4‐hydroxyphenyl)‐1,2,4,5‐tetrazine which was then subjected to esterification reaction with 3,4,5‐tris(dodecyloxy)benzoic acid. The chemical structure of the sym‐tetrazine gelator was confirmed by elemental analysis, fourier‐transform infrared spectroscopy (FT‐IR), and nuclear magnetic resonance (¹H‐ and ¹³C‐NMR) spectral measurements. It was confirmed to exhibit relatively strong gelation ability to produce supramolecular assemblies in several polar alcoholic organic solvents, such as butanol, octanol, and 1,6‐dihydroxyhexane. The π‐π stacking and van der Waals mediated self‐assembly of tetrazine‐based organogelator were studied by scanning electron microscopy images of the xerogel to reveal that the obtained organogel consists of fibrillar aggregates. Investigation of FT‐IR and concentration‐dependent ¹H‐NMR spectra confirm that the intermolecular van der Waals interactions and π‐π stacking were the key driving forces for self‐assembly during gelation process of s‐tetrazine molecules.