Simple Development of Novel Reversible Colorimetric Thermometer Using Urea Organogel Embedded with Thermochromic Hydrazone Chromophore

Abstract

Thermochromic urea (U) organogel immobilized with a thermochromic tricyanofuran hydrazone (TCFH) chromophore was developed. Thermochromic TCFH chromophore bearing two nitro functional groups on a hydrazone recognition unit was synthesized via an azo-coupling reaction of tricyanofuran (TCF) heterocyclic moiety containing an active methyl group with the diazonium chloride salt of 2,4-dinitroaniline comprising two strongly electron-withdrawing nitro groups. The molecular structure of both intermediates and TCFH dye were characterized by several analytical methods, including 1H NMR, 13C NMR, IR, mass spectroscopy (MS), and elemental analysis. The thermochromic responsiveness could be attributed to the charge delocalization of TCFH as well as to the presence of an intramolecular charge transfer. The generated organogel displayed a thermoreversible sol–gel transition associated with color change. The origin of the monitored thermochromism is a conformational change of the tricyanofuran hydrazone backbone due to the temperature-driven deprotonation–protonation reversible process. The prepared urea–tricyanofuran hydrazone (UTCFH) thermometer acted as a diagnostic tool providing an instant color change between yellow, orange, red and purple upon changing the temperature of the UTCFH organogel in dimethyl sulfoxide (DMSO). This color change was proportionally correlated with increasing the temperature from 44 to 63 °C. The UTCFH organogel composed of urea and push-π-pull hydrazone type tricyanofuran chromophore immobilized physically in the urea organogel was found to function as a temperature-driven chromic thermometer. This chromogenic UTCFH organogel in DMSO displayed a phase transition at 41–48 °C. The morphological properties of the gel internal fibrous nanostructure (80–120 nm) were monitored by scanning electron microscopy (SEM). The colorimetric measurements were monitored by UV–Vis absorption spectroscopy. The chromogenic thermometer demonstrated a good reversibility without fatigue. The mechanism accounting for thermochromism of UTCFH organogel is proposed.