Colorimetric Polydiacetylene Nanotubes from Self-Assembly of a Barbituric Acid-Derived Diacetylene

Abstract

Covalent organic nanotubes offer enhanced stability, robustness, and functionality, compared to their noncovalent counterparts. This study explores constructing polydiacetylene (PDA) nanotubes using a two-step process: self-assembly via noncovalent interactions followed by UV-induced polymerization of a diacetylene template. A promising building block PCDA-BA consisting of a hydrogen-bonding headgroup, barbituric acid, linked to a linear diacetylene chain was prepared. Through self-complementary hydrogen bonding arising from barbituric acid and π-π stacking of diacetylene template directs molecular ordering to form a tapelike molecular arrangement, which then transforms to bilayer lamellar sheets that scroll into nanotubes with increasing solvent polarity. Fourier transform infrared spectroscopy and powder X-ray diffraction patterns show both single-wall and multiple-wall nanotubes, depending on the scrolling pathway. These noncovalent structures convert into covalently linked blue-phase chromogenic nanotubes (P(PCDA-BA)) via UV-induced polymerization. The blue phase P(PCDA-BA) shows promising potential as a colorimetric sensor material with significant reversible thermoreversibility up to 160 °C for multiple thermal cycles and hydrazine sensing capabilities. This study highlights the significance of molecular integration design in constructing covalent nanotubes with chromogenic properties.