Covalently Linked Perylene Diimide-Polydiacetylene Nanofibers Display Enhanced Stability and Photocurrent with Reversible FRET Phenomenon.

Because of their unique structural and optical properties, 1D perylene diimide (PDI) derivatives have gained attention for use in optoelectronic devices. However, PDI-containing self-assembled supramolecular systems often are of limited use because they have supramolecular architectures that are held together by weak noncovalent π-π stacking, hydrogen bonding, and hydrophobic interactions. As a result, they are intrinsically unstable under solution-processing conditions. To overcome this limitation, a polydiacetylene (PDA)-based strategy is developed to construct a solvent-resistant and stable PDI assembly. For this purpose, first the monomer PDI-BisDA is generated, in which two polymerizable diacetylene (DA) units are covalently linked to a PDI core. Importantly, 254 nm UV irradiation of self-assembled PDI-BisDA nanofibers forms solvent-resistant and stable PDI-PDA fibers. Owing to the presence of PDA, the generated polymer fibers display an increased photocurrent. In addition, the existence of PDA and PDI moieties in the fiber leads to the occurrence of switchable on-off fluorescence resonance energy transfer (FRET) between the PDI and reversibly thermochromic PDA chromophores.

Reversibly Thermochromic Cyclic Dipeptide Nanotubes.

Owing to their capability of forming extensive hydrogen bondings and the facile introduction of chirality, cyclic dipeptides (CDPs) have gained great attention as scaffolds for functional supramolecules. Surprisingly, introduction of a photopolymerizable diacetylene (DA) moiety to the CDP afforded nanotubular structures with enhanced stability and reversible thermochromism. A series of CDP-containing DAs (CDP-DAs) are prepared by coupling 10,12-pentacosadiynoic acid with CDPs, cyclo(-Gly-Ser) and cis/trans cyclo(-Ser-Ser). Fabrication of CDP-DA self-assemblies in a polar chloroform and methanol solvent mixture affords nanotubes comprising single-wall and multiwall structures. The self-assembly behavior and morphology characteristic are examined by scanning electron microscopy and transmission electron microscopy. Next, X-ray diffraction analysis confirms well-ordered lamellar structures with a perfect agreement with the bilayer formation leading to the tubular structure via lamellar scrolling behavior. Upon UV irradiation, monomeric CDP-DA tubular assemblies result in the blue-colored CDP/polydiacetylene (PDA) nanotubes. Interestingly, CDP/PDA nanotubes exhibit a reversible blue-to-red color change for over 10 consecutive thermal cycles. The CDP-DA/PDA supramolecular system demonstrates potential applications in developing stimulus-responsive functional materials.